Resin composition, cured product, laminate, method for producing cured product, method for producing laminate, method for producing semiconductor device, semiconductor device, and resin

Abstract

Provided are: a resin composition which contains a resin having a polymerizable group and a photopolymerization initiator, wherein the resin has at least one partial structure represented by formula (A-1a) or formula (A-1b), and the proportion of the molar amount of a cyclobutane ring having a trans-type steric conformation to the total molar amount of cyclobutane rings contained in the resin is 80% or more; a cured product which is obtained by curing the composition and a method for producing the cured product; a laminate which contains the cured product and a method for producing the laminate; a semiconductor device and a method for producing the semiconductor device; and a novel resin.

Description

Resin composition, cured product, laminate, method for manufacturing a cured product, method for manufacturing a laminate, method for manufacturing a semiconductor device, semiconductor device, and resin

[0001] The present invention relates to resin compositions, cured products, laminates, methods for producing cured products, methods for producing laminates, methods for producing semiconductor devices, semiconductor devices, and resins.

[0002] In modern times, resin materials manufactured from resin compositions containing resins are utilized in various fields. For example, resins such as polyimide are used in a wide range of applications due to their excellent heat resistance and insulation properties. While not limited to these applications, examples of applications in semiconductor devices for packaging include their use as insulating films, encapsulating materials, or protective films. They are also used as base films and coverlays for flexible substrates.

[0003] For example, in the applications described above, resins such as polyimide are used in the form of a resin composition containing a resin such as a polyimide precursor. Such a resin composition can be applied to a substrate, for example by coating, to form a resin film, and then, if necessary, exposure, development, heating, etc., can be performed to form a cured product on the substrate. Since the resin composition can be applied by known methods, it can be said that it has excellent manufacturing adaptability, such as a high degree of freedom in designing the shape, size, and application position of the resin composition when applied. In addition to the high performance of resins such as polyimide, the industrial application development of the above-mentioned resin composition is increasingly expected from the viewpoint of such excellent manufacturing adaptability.

[0004] For example, Patent Document 1 describes a polyimide obtained from 1,2,3,4-cyclobutanetetracarboxylic dianhydride (hereinafter sometimes abbreviated as CBDA) and a diamine compound containing specific structural units. Patent Document 2 describes a polyimide resin containing a specific combination of structural units.

[0005] Japanese Patent Publication No. 2010-007034, International Publication No. 2017 / 051783

[0006] From the perspective of avoiding the formation of reverse tapered patterns, and from the perspectives of speeding up the manufacturing process and saving energy, there is a need for resin compositions that can form patterns even with low exposure. In the present invention, a resin composition that can form patterns with low exposure is referred to as a "resin composition with excellent curability."

[0007] The present invention aims to provide a resin composition with excellent curability, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product. The present invention also aims to provide a novel resin.

[0008] Examples of typical embodiments of the present invention are shown below. <1> A resin composition comprising a polymerizable resin and a photopolymerization initiator, wherein the resin has at least one of a substructure represented by formula (A-1a) and a substructure represented by formula (A-1b), and the ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin is 80% or more. In formula (A-1a), X １ Y represents a cyclobutane ring. １ represents a divalent organic group. In formula (A-1b), X １ Y represents a cyclobutane ring. １ R indicates a divalent organic group, １ and R ２ Each independently represents a hydrogen atom or a monovalent organic group. <2> The resin composition according to <1>, wherein the ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin is 95 to 99%. <3> The resin composition according to <1> or <2>, wherein the total content of the substructures represented by formula (A-1a) or formula (A-1b) relative to the total repeating units in the resin is 50 mol% or more. <4> The resin contains at least one substructure selected from the group consisting of the substructure represented by formula (A-11), the substructure represented by formula (A-12), formula (A-13), and the substructure represented by formula (A-14), in formula (A-11), X１１ represents a cyclobutane ring. In formula (A-12), X １１ represents a cyclobutane ring, R １ and R ２ each represent a hydrogen atom or a monovalent organic group. In formula (A-13), X １１ represents a cyclobutane ring, R １ each represent a hydrogen atom or a monovalent organic group. In formula (A-14), X １１ represents a cyclobutane ring, R ２ each represent a hydrogen atom or a monovalent organic group. Among all X １１ contained in the above resin, the proportion of the molar amount of the cyclobutane ring in the trans conformation is 80 mol% or more. The resin composition according to any one of <1> to <3>. <5> The resin has a partial structure represented by the above formula (A-1a). As the partial structure represented by the above formula (A-1a), it has a partial structure represented by the following formula (A-2a1) and a partial structure represented by (A-2b1). The resin composition according to any one of <1> to <4>. In formula (A-2a1), Ya ２ represents a structure represented by the following formula (Y-1), Ay ２ represents a group represented by formula (Z-1), and n2 is an integer of 1 or 2. In formula (A-2b1), Yb ２ represents a structure represented by the following formula (Y-2). In formula (Y-1), Ar １ represents an aromatic group having 6 to 10 carbon atoms which may have a substituent, L １ represents a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ - or -CR ４ ２ represents, Y １Ar represents an aromatic group having 6 to 30 carbon atoms, which may have substituents. １ and Y １ At least one of them is Ay as a substituent. ２ It has bonding sites with, where a represents an integer from 0 to 3, and * represents the bonding site with the nitrogen atom. In formula (Y-2), Ar ２ L represents an aromatic group having 6 to 10 carbon atoms, which may have substituents. ２ The bond is a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ - or -NR ３ (C=O)NR ２ - indicates Y ２ represents an aromatic group having 6 to 30 carbon atoms, which may have substituents, b represents an integer from 0 to 3, and * represents a bonding site with a nitrogen atom. In formula (Z-1), Lx １ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates Lx ２ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２-、-NR ２ (C=O)NR ３ -、-NR ３ (C=O)NR ２ -、-CH ２ CH(OH)-CH ２ -、or、-CH ２ CH(OR ５ )-CH ２ - represents, R １ represents a hydrogen atom or a monovalent organic group, R ２ represents a hydrogen atom or a monovalent organic group, R ３ represents a hydrogen atom or a monovalent organic group, R ４ represents a hydrogen atom or a monovalent organic group, R ５ represents a monovalent organic group, La represents a group represented by the following formula (La-1), Lb represents a hydrocarbon group with r4+1 valences having 1 to 12 carbon atoms, a group consisting of any one or a combination of the following formulas (Lb-1) to (Lb-3), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r1 represents 0 or 1, r2 represents 0 or 1, r3 represents an integer from 0 to 5, r4 represents an integer from 1 to 10, * represents Ar of formula (Y-1) １ or Y １ indicates the bonding site with. In formula (La-1), Ra １ , Ra ２ each independently represents a hydrogen atom, an alkyl group or an aryl group, * represents the bonding site with Lx １ and the wavy line represents the bonding site with any one of Lx ２ , Lb or A, respectively. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms or a combination thereof, and x, y, z each independently represents an integer from 1 to 30. <6> The resin composition according to any one of <1> to <5>, wherein the resin has a partial structure represented by the following formula (A-2a2) and a partial structure represented by the following formula (A-2b2) as the partial structure represented by the above formula (A-1b). In formula (A-2a2), Ya ２ represents a structure represented by the following formula (Y-3), R ５１ , R ５２ , Ay３ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or the following formula (Z-2). n3 is an integer from 0 to 3, and when n3 = 0, R ５１ , R ５２ at least one of which represents a group represented by the formula (Z-2). In the formula (A-2b2), Yb ２ represents a divalent organic group, and R ５１ , R ５２ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or the following formula (Z-2). In the formula (Y-3), Ar ３ represents an aromatic group having 6 to 10 carbon atoms which may have a substituent, and L ３ represents a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, or -NR ３ (C=O)NR ２ -, Y ３ represents an aromatic group having 6 to 30 carbon atoms which may have a substituent, and at least one of Ar ３ and Y ３ has a bonding site with Ay ３ as a substituent, a represents an integer from 0 to 3, and * represents a bonding site with a nitrogen atom. In the formula (Z-2), Lx １ represents -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH２ CH(OR ５ ) - CH ２ - indicates Lx ２ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates R １ R represents a hydrogen atom or a monovalent organic group. ２ R represents a hydrogen atom or a monovalent organic group. ３ R represents a hydrogen atom or a monovalent organic group. ４ R represents a hydrogen atom or a monovalent organic group. ５ represents a monovalent organic group, La represents the group shown in the following formula (La-1), Lb represents a C1-C12 r4+1 valent hydrocarbon group, a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r1 represents 0 or 1, r2 represents 0 or 1, r3 represents an integer from 0 to 5, r4 represents an integer from 1 to 10, and * represents Ar of formula (Y-3). ３ or Y ３ This shows the binding site. In formula (La-1), Ra １ , Ra ２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and * represents Lx １ The wavy line indicates the connection point with Lx ２ The binding sites with either Lb or A are shown, respectively. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z each independently represent an integer from 1 to 30. <7> The resin composition according to any one of <1> to <6>, wherein the resin has a structure represented by the following formula (M-1) or (M-2). In formula (M-1) or formula (M-2), L １ L represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3). ２ R indicates a single bond or an organic group with (k+1) valency. ２１ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a group containing any of the following: an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r represents 0 or 1, k represents an integer from 1 to 6, and * represents Y １ This shows the binding site. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z represent integers from 0 to 30. <8> In the above formula (M-1) or (M-2), L １ The resin composition according to <7>, wherein the resin is represented by any of the above formulas (Lb-1), (Lb-2), or (Lb-3), or a combination thereof. <9> The resin is Y in the above formula (A-1a) or (A-1b). １ The resin composition according to any one of <1> to <8>, comprising at least one of the structures represented by the following formula (Y1-1) or formula (Y1-2). In equation (Y1-1), Ay １１ and Ay １２ Each independently represents a group having a polymerizable group, and m1 and m2 independently represent integers from 0 to 2, R ２１ and R ２２ Each of these independently represents one of an alkyl group, an aryl group, a halogen atom, or a trifluoromethyl group, n1 is an integer from 0 to (4-m1), n2 is an integer from 0 to (4-m2), and L is a single bond, -CR １ R２ -, -C=C-, -O-, -(C=O)-, -NH-(C=O)-, -(C=O)O-, -S(=O)-, -S(=O) ２ - indicates R １ and R ２ Each of the following independently represents a hydrogen atom, an alkyl group, an aryl group, or a trifluoromethyl group, and * indicates a bonding site with other structures. In formula (Y1-2), Ay １３ indicates a group having a polymerizable group, m3 is an integer from 0 to 2, and R ２３<10> A resin composition according to any one of <1> to <9>, wherein the photopolymerization initiator is a photoradical polymerization initiator. <11> A resin composition according to any one of <1> to <10>, wherein the photopolymerization initiator is a (keto)oxime ester compound. <12> A resin composition according to any one of <1> to <11>, comprising a polyfunctional polymerizable compound different from the above resin. <13> A resin composition according to any one of <1> to <12>, comprising an amine compound. <14> A resin composition according to any one of <1> to <13>, used for forming an interlayer insulating film for a redistribution layer. <15> A cured product obtained by curing the resin composition according to any one of <1> to <14>. <16> A laminate comprising two or more layers made of the cured product described in <15>, with a metal layer between any of the layers made of the cured product. <17> A method for manufacturing a cured product, comprising a film forming step of applying the resin composition described in any one of <1> to <14> onto a substrate to form a film. <18> A method for manufacturing a cured product according to <17>, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern. <19> A method for manufacturing a cured product according to <17>, comprising a heating step of heating the film at 50 to 450°C. <20> A method for manufacturing a laminate, comprising the method for manufacturing a cured product described in any one of <17> to <19>. <21> A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product described in any one of <17> to <19>. <22> A semiconductor device comprising the cured product described in <15>. <23> A resin having a substructure represented by formula (A-3a) or a substructure represented by formula (A-3b), wherein the ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin is 80% or more. In formula (A-3a), X １ Y represents a cyclobutane ring. １X represents a divalent organic group having at least one polymerizable group selected from the group consisting of (meth)acrylic group, vinylphenyl group, epoxy group, oxetane group, group having an ethylenically unsaturated bond, and maleimide group. In formula (A-3b), X １ Y represents a cyclobutane ring. １ R represents a divalent organic group having at least one polymerizable group selected from the group consisting of (meth)acrylic group, vinylphenyl group, epoxy group, oxetane group, group having an ethylenically unsaturated bond, and maleimide group, １ and R ２ Each independently represents a hydrogen atom or a monovalent organic group. <24> The resin according to <23>, wherein the total content of the substructure represented by formula (A-3a) or formula (A-3b) is 50 mol% or more with respect to the total repeating units of the resin.

[0009] The present invention provides a resin composition with excellent curability, a cured product obtained by curing the resin composition, a laminate containing the cured product, a method for manufacturing the cured product, a method for manufacturing the laminate, a method for manufacturing a semiconductor device including the method for manufacturing the cured product, and a semiconductor device containing the cured product. Furthermore, the present invention provides a novel resin.

[0010] The main embodiments of the present invention will be described below. However, the present invention is not limited to the embodiments explicitly stated. In this specification, numerical ranges represented by the symbol "~" mean a range that includes the numerical values ​​before and after "~" as the lower and upper limits, respectively. In this specification, the term "process" includes not only independent processes but also processes that are indistinguishable from other processes as long as the intended effect of the process is achieved. In the notation of groups (atomic groups) in this specification, notations that do not specify substituted or unsubstituted include both groups (atomic groups) with substituents and groups (atomic groups) without substituents. For example, "alkyl group" includes not only alkyl groups without substituents (unsubstituted alkyl groups) but also alkyl groups with substituents (substituted alkyl groups). In this specification, "exposure" includes not only exposure using light but also exposure using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include the emission line spectrum of mercury lamps, far ultraviolet light represented by excimer lasers, extreme ultraviolet (EUV) light, X-rays, electron beams, and other active light or radiation. In this specification, "(meth)acrylate" means both or either "acrylate" and "methacrylate," "(meth)acrylic" means both or either "acrylic" and "methacrylic," and "(meth)acryloyl" means both or either "acryloyl" and "methacryloyl." In this specification, Me in structural formulas represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group. In this specification, total solids means the total mass of all components of the composition excluding the solvent. In this specification, solids concentration is the mass percentage of the components other than the solvent relative to the total mass of the composition. In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​measured using gel permeation chromatography (GPC) and are defined as polystyrene equivalent values, unless otherwise specified.In this specification, weight-average molecular weight (Mw) and number-average molecular weight (Mn) can be determined, for example, by using an HLC-8220GPC (manufactured by Tosoh Corporation) and connecting Guard Column HZ-L, TSKgel Super HZM-M, TSKgel Super HZ4000, TSKgel Super HZ3000, and TSKgel Super HZ2000 (all manufactured by Tosoh Corporation) in series as columns. Unless otherwise specified, these molecular weights shall be measured using NMP (N-methyl-2-pyrrolidone) as the eluent. However, if NMP is unsuitable as an eluent, such as in cases of low solubility, THF (tetrahydrofuran) may be used. Unless otherwise specified, detection in GPC measurements shall be performed using a UV (ultraviolet) wavelength 254 nm detector. In this specification, when the positional relationship of each layer constituting a laminate is described as "up" or "down," it is sufficient that there are other layers above or below the reference layer among the multiple layers of interest. That is, a third layer or element may be interposed between the reference layer and the other layers, and the reference layer and the other layers do not need to be in contact. Unless otherwise specified, the direction in which layers are stacked on the substrate is referred to as "up," or, if there is a resin composition layer, the direction from the substrate to the resin composition layer is referred to as "up," and the opposite direction is referred to as "down." Note that this setting of up and down directions is for convenience in this specification, and in actual embodiments, the "up" direction in this specification may differ from vertically upward. In this specification, unless otherwise specified, a composition may contain two or more compounds corresponding to each component contained in the composition. Also, unless otherwise specified, the content of each component in the composition means the total content of all compounds corresponding to that component. In this specification, unless otherwise specified, the temperature is 23°C, the atmospheric pressure is 101,325 Pa (1 atmosphere), and the relative humidity is 50% RH. In this specification, preferred embodiments are more preferred embodiments.

[0011] The resin composition of the present invention (hereinafter also simply referred to as "resin composition") contains a resin having polymerizable groups and a photopolymerization initiator, wherein the resin has at least one of the substructures represented by formula (A-1a) and (A-1b), and the ratio of the molar amount of trans-conformation cyclobutane rings to the total molar amount of cyclobutane rings contained in the resin is 80% or more. Hereinafter, a resin having at least one substructure selected from the group consisting of the substructure represented by formula (A-1a) and the substructure represented by formula (A-1b), and having polymerizable groups, in which the ratio of the molar amount of trans-conformation cyclobutane rings to the total molar amount of cyclobutane rings contained is 80% or more, will also be referred to as "specific resin". In formula (A-1a), X １ Y represents a cyclobutane ring. １ represents a divalent organic group. In formula (A-1b), X １ Y represents a cyclobutane ring. １ R indicates a divalent organic group, １ and R ２ Each of these independently represents either a hydrogen atom or a monovalent organic group.

[0012] The resin composition of the present invention is preferably used to form a photosensitive film subjected to exposure and development, and more preferably used to form a photosensitive film subjected to exposure and development using a developer containing an organic solvent. The resin composition of the present invention can be used, for example, to form insulating films for semiconductor devices, interlayer insulating films for redistribution layers, stress buffer films, etc., and is preferably used to form interlayer insulating films for redistribution layers. Furthermore, the resin composition of the present invention is preferably used to form a photosensitive film subjected to negative-type development. In the present invention, negative-type development refers to development in which unexposed areas are removed by development during exposure and development, and positive-type development refers to development in which exposed areas are removed by development. As the exposure method, developer, and development method described above, for example, the exposure method, developer, and development method described in the exposure step, development step, etc., described later in the description of the method for manufacturing cured products may be used.

[0013] The resin composition of the present invention exhibits excellent curability. Although the mechanism by which the above effect is obtained is unknown, it is presumed to be as follows.

[0014] Conventional polyimides use resins containing aromatic rings in the acid anhydride unit (for example, references 1-2). However, the present inventors have found that in conventional polyimides containing aromatic rings in the acid anhydride unit, the absorption of exposure light such as UV (ultraviolet) light by the aromatic ring is large, making it difficult to sufficiently expose the film to its depths, and there is room for improvement in curability. The resin composition of the present invention comprises a resin having a substructure represented by formula (A-1a) or formula (A-1b) which has polymerizable groups and a structure containing a cyclobutane ring, and a photopolymerization initiator. Since the cyclobutane ring absorbs less UV light than the aromatic ring, for example, the transmittance of UV light in a film made of the resin composition increases, making it easier to expose the film to its depths, and the photopolymerization initiator is sufficiently photosensitive even in the depths, so polymerization of the polymerizable groups proceeds sufficiently. Furthermore, the inclusion of a trans-conformed cyclobutane ring, which has higher mobility compared to aromatic rings, facilitates the orientation of the resin's crosslinking groups and increases the resin's crystallinity, thus improving the curability of the resin composition. Additionally, the inclusion of a trans-conformed cyclobutane ring restricts the structural mobility, which is thought to lower the coefficient of thermal expansion. In particular, when a certain amount of cis conformation is included, the resin's Tg becomes lower and softer, increasing the solubility of unexposed areas during exposure and development, thus improving the developability of the resin composition.

[0015] Here, the trans and cis conformations as used herein will be explained. The trans conformation of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CBDA) is represented by the following formula (Cy-1), and the cis conformation of CBDA is represented by the following formula (Cy-2). That is, the trans conformation is described as having two pairs of acid anhydride groups facing opposite directions relative to the central cyclobutane ring, and the cis conformation is described as having two pairs of acid anhydride groups facing the same direction relative to the central cyclobutane ring. When a cyclic structure is described without particularly limiting stereoisomers by means of a wedge bond or a prefix, it means that the stereoisomers are not particularly limited.

[0016] Also, Patent Documents 1 to 2 do not describe or suggest a resin composition containing a resin corresponding to a specific resin. The "cis, trans, cis form" described in Patent Documents 1 to 2 has the same geometric isomer structure as the trans conformation in this specification. Also, the trans conformation in this specification has the same geometric isomer structure as "cis-trans-cis form" in Figure 6 described in the document "Journal of Polymer Science: Part A: Polymer Chemistry, Vol. 38, 108-116 (2000)" cited by Patent Documents 1 to 2.

[0017] Hereinafter, the components contained in the resin composition of the present invention will be described in detail.

[0018] <Specific Resin> The resin composition of the present invention is a resin having a polymerizable group and contains a resin (specific resin) having at least one partial structure selected from the group consisting of a partial structure represented by formula (A-1a) and a partial structure represented by formula (A-1b).

[0019] The specific resin is preferably a polyimide or a polyimide precursor. When the specific resin is a polyimide, the specific resin preferably has a partial structure represented by formula (A-1a) described later, and preferably has a partial structure represented by formula (A-1a) as a repeating unit. When the specific resin is a polyimide precursor, the specific resin preferably has a partial structure represented by formula (A-1b) described later, and preferably has a partial structure represented by formula (A-1b) as a repeating unit.

[0020] It is one preferred embodiment that the specific resin has a structure having a cyclobutane ring only in X １ in formula (A-1a) or formula (A-1b).

[0021] In this specification, polyimide refers to a resin having repeating units containing imide structures within its molecular chain, and preferably a resin having repeating units containing imide ring structures within its molecular chain. Furthermore, if the polyimide is a linear resin, it is preferable that the polyimide is a resin having repeating units containing imide structures within its main chain, and more preferably a resin having repeating units containing imide ring structures within its main chain. In this specification, "main chain" refers to the relatively longest bonding chain in the resin molecule, and "side chains" refer to the other bonding chains. In this specification, imide structure refers to a structure represented by *-C(=O)N(-*)C(=O)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. In this specification, imide ring structure refers to a ring structure that includes all two carbon atoms and nitrogen atoms in the above imide structure as ring members. The imide ring structure is preferably a five-membered ring. In addition to the imide structure, polyimide may also be a so-called polyamide imide, which has amide bonds within its molecular chain. In this specification, an amide bond refers to a structure represented by *-C(=O)N(-#)-*, where * represents a bonding site with another structure, preferably a bonding site with a carbon atom, and more preferably a bonding site with a quaternary carbon atom. Also, # represents a bonding site with another structure, preferably a bonding site with a hydrogen atom or a carbon atom, and more preferably a bonding site with a hydrogen atom.

[0022] In this specification, a polyimide precursor refers to a resin that undergoes a change in chemical structure due to external stimuli to become a polyimide, preferably a resin that undergoes a change in chemical structure due to heat to become a polyimide, and more preferably a resin that undergoes a ring-closing reaction due to heat to form a ring structure to become a polyimide.

[0023] [Polymerizable Groups] The specific resin has polymerizable groups. Radical polymerizable groups are preferred. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, etc., with groups having ethylenically unsaturated bonds being preferred. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, vinylphenyl groups, (meth)acryloyl groups, maleimide groups, and groups having a norbornene skeleton. Among these, (meth)acryloyl groups, vinylphenyl groups, or maleimide groups are preferred, and from the viewpoint of reactivity, (meth)acryloyl groups are more preferred. From the viewpoint of reducing dielectric loss tangent, vinylphenyl groups or maleimide groups are preferred. The (meth)acryloyl group is preferably composed of a (meth)acryloxy group or a (meth)acrylamide group, and from the viewpoint of reactivity, it is more preferred to be composed of a (meth)acryloxy group. From the viewpoint of adhesion, the hydrophobic vinylphenyl group is preferred. Furthermore, it is preferable that the resin has the following formula (M-1) or the following formula (M-2) as a partial structure containing polymerizable groups. １ However, it is more preferable that it be represented by any of the following formulas (Lb-1), (Lb-2), or (Lb-3), or a combination thereof. In formula (M-1), L １ L represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3). ２ R indicates a single bond or an organic group with (k+1) valency. ２１ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a group containing any of an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r represents 0 or 1, k represents an integer from 1 to 6, and * represents a bonding site with other structures. In formula (M-2), L １ L represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3). ２represents a single bond or a (k + 1)-valent organic group, and R ２１ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a group containing any one of an epoxy group, an oxenyl group, and a group having an ethylenic unsaturated bond, k represents an integer of 1 to 6, and * represents a bonding site with another structure. In formulas (Lb-1) to (Lb-3), Lc １ represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z represent integers of 0 to 30.

[0024] In formula (M-1), L １ is preferably an alkylene group having 1 to 12 carbon atoms, a phenylene group, or a group composed of any one or a combination of formulas (Lb-1) to (Lb-3), and more preferably an alkylene group having 2 to 6 carbon atoms, a phenylene group, or a group composed of any one or a combination of formulas (Lb-1) to (Lb-3). Also, L １ is preferably a group represented by formulas (Lb-1) to (Lb-3), or a group represented by a combination thereof, and also preferably a group represented by formula (Lb-1), formula (Lb-2), or a combination thereof. Lc1 in formulas (Lb-1) to (Lb-3) is preferably an alkylene group having 2 to 8 carbon atoms, an arylene group having 6 to 10 carbon atoms, or a combination thereof, and more preferably an alkylene group having 2 to 8 carbon atoms. In formulas (Lb-1) to (Lb-3), x, y, and z each independently represent an integer of 1 to 30, preferably an integer of 1 to 20, and more preferably an integer of 1 to 10.

[0025] In formula (M-1), L ２ represents a single bond or a (k + 1)-valent organic group, preferably a single bond or a saturated aliphatic hydrocarbon group having 2 to 10 carbon atoms or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and more preferably a single bond or a saturated aliphatic hydrocarbon group having 2 to 6 carbon atoms. The hydrogen atoms in the above saturated aliphatic hydrocarbon group or aromatic hydrocarbon group may be substituted by known substituents.

[0026] In formula (M-1), R ２１The hydrogen atom or an alkyl group having 1 to 10 carbon atoms is preferred, a hydrogen atom or an alkyl group having 1 to 4 carbon atoms is more preferred, and a hydrogen atom or a methyl group is even more preferred.

[0027] In formula (M-1), A is preferably a group having an ethylenically unsaturated bond, and is preferably a (meth)acryloyl group, a vinylphenyl group, or a maleimide group. Other known groups having an ethylenically unsaturated bond, such as a vinyl group or an allyl group, may also be used.

[0028] In formula (M-1), k is more preferably an integer between 1 and 3, and even more preferably 1 or 2. Furthermore, k being 1 is also one of the preferred embodiments of the present invention.

[0029] In formula (M-1), * is preferably a bonding site with a carbon atom, and more preferably a bonding site with a carbon atom included in the main chain of a specific resin.

[0030] In formula (M-2), L １ , L ２ , R ２１ A preferred embodiment of A, k and * is L in formula (M-1). １ , L ２ , R ２１ This is similar to the preferred embodiments of A, k, and *.

[0031] The content of polymerizable groups relative to the total mass of the specific resin (polymerizability value) is preferably 0.2 to 4.0 mmol / g, more preferably 0.5 to 3.5 mmol / g, and even more preferably 1.0 to 3.4 mmol / g. In particular, the content of radical polymerizable groups relative to the total mass of the specific resin (radical polymerizability value) is preferably 0.2 to 4.0 mmol / g, more preferably 0.5 to 3.5 mmol / g, and even more preferably 0.5 to 1.0 mmol / g. For example, the content of vinylphenyl groups in the resin in the composition can be calculated by the following method. The calculation method is the same for other polymerizable groups and radical polymerizable groups. 1 g of the composition is added to 50 g of methanol or water and crystallized to precipitate the specific resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours. After dissolving 0.1 g of the dried specific resin described above in 0.9 g of didimethyl sulfoxide, １ The amount of vinylphenyl groups is calculated by measuring with 1H-NMR. １ The number of 1H-NMR scans will be 640. For example, tetramethylsilane will be used as the reference substance. １ The molar amount of vinylphenyl groups in a specific resin can be calculated from the ratio of the integrated intensity of the peak around 5.0–7.0 ppm derived from vinylphenyl groups in the 1H-NMR chart to the integrated intensity of the peak derived from the reference substance, the amount of the reference substance, and the amount of the specific resin. The molar amounts of other structures can also be measured by calculating the integrated intensity of the peaks corresponding to each structure.

[0032] [Substructure] The specified resin has at least one substructure selected from the group consisting of the substructure represented by formula (A-1a) and the substructure represented by formula (A-1b).

[0033] [Substructure represented by formula (A-1a)] -X １ - In formula (A-1a), X １This represents a cyclobutane ring. The ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin is preferably 80% or more, and particularly preferably 95% or more. There is no particular upper limit, but it is preferably 99% or less. In addition, all X in all substructures represented by formula (A-1a) contained in the specific resin １ In the total cyclobutane ring represented by , the proportion of the molar amount of the trans conformational cyclobutane ring is preferably 80% or more, and particularly preferably 95% or more. There is no particular upper limit, but it is preferably 99% or less. The trans conformational cyclobutane ring described herein differs from the "Trans" described in Patent Documents 1 and 2, and refers to a ring in which two pairs of imide rings are oriented in opposite directions relative to the central cyclobutane ring. The cyclobutane ring of the "cis,trans,cis" described in Patent Documents 1 and 2 is equivalent to the trans conformational cyclobutane ring described herein. In the trans conformational cyclobutane ring described herein, the hydrogen atoms bonded to the cyclobutane ring may be substituted with alkyl groups, and these alkyl groups may be bonded to each other to form a 5- or 6-membered ring structure. However, X described in formula (A-1a) １ The four carbonyl groups bonded to it are X １ In this structure, the carbon atom, which is a member atom of the cyclobutane ring, is bonded to the central cyclobutane ring by a single bond without a linking group. Even when substituted with an alkyl group, whether it is in trans or cis conformation is determined solely by the orientation of the two paired imide rings bonded to the central cyclobutane ring. Note that when the ring structure is described without specifying a wedge bond or prefix to limit the stereoisomer, it means that the stereoisomer is not particularly limited. The ratio of trans-conformed cyclobutane rings to cis-conformed cyclobutane rings is: １ This can be calculated by H-NMR. The ratio of cyclobutane rings in the cis conformation to cyclobutane rings in the trans conformation is: １ H-NMR (C ２ D ３ In N, it can be identified by the ratio of the integral value at δ3.75 (d, 4H) to the integral value at δ3.86 (s, 4H).

[0034] -Y １ - Y １ It is preferable that the structure is derived from a diamine monomer, but is not limited thereto. The diamine monomer is not particularly limited as long as it has two primary amino groups in one molecule. It may be an aromatic diamine, an aliphatic diamine, or a mixture thereof. In formula (A-1a), Y １ This indicates a divalent organic group. Y １ Preferably, it includes at least a structure represented by the following formula (Y1-1) or the following formula (Y1-2). In equation (Y1-1), Ay １１ and Ay １２ Each independently represents a group having a polymerizable group, and m1 and m2 independently represent integers from 0 to 2, R ２１ and R ２２ Each of these independently represents one of an alkyl group, an aryl group, a halogen atom, or a trifluoromethyl group, n1 is an integer from 0 to (4-m1), n2 is an integer from 0 to (4-m2), and L is a single bond, -CR １ R ２ -, -C=C-, -O-, -(C=O)-, -NH-(C=O)-, -(C=O)O-, -S(=O)-, -S(=O) ２ - indicates R １ and R ２ Each of the following independently represents a hydrogen atom, an alkyl group, an aryl group, or a trifluoromethyl group, and * indicates a bonding site with other structures. In formula (Y1-2), Ay １３ indicates a group having a polymerizable group, m3 is an integer from 0 to 2, and R ２３ represents one of the alkyl group, aryl group, halogen atom, or trifluoromethyl group, n3 is an integer from 0 to (4-m3), and * indicates a bonding site with other structures.

[0035] <<Ay １１ Ay １２ >> In formula (Y1-1), Ay １１ and Ay １２Each of these is preferably an independent group represented by formula (M-1) or formula (M-2) above, and more preferably an independent group represented by formula (M-1). Also, in formula (Y1-1), Ay １１ and Ay １２ Preferably, each of these is an independent group represented by formula (Z-1) described later.

[0036] <<m1, m2>> In formula (Y1-1), m1 and m2 are each independently preferably 1 or 2, and more preferably 1.

[0037] <<R ２１ , R ２２ >> In formula (Y1-1), R ２１ and R ２２ Each of these is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a fluorine atom, or a trifluoromethyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorine atom, or a trifluoromethyl group.

[0038] <<n1, n2>> In equation (Y1-1), n1 and n2 are each independently integers between 0 and 2, and more preferably 0 or 1.

[0039] <<L>> In equation (Y1-1), L is a single bond, -CR １ R ２ -, -C(R ３１ R ４１ )-C(R ３２ R ４２ )-,-CR ５１ =CR ５２ -, -C≡C-, -O-, -(C=O)-, -NH-(C=O)-, -(C=O)O-, -S(=O)-, -S(=O) ２ - indicates a single bond, -CR １ R ２ -, -O- or -(C=O)- is preferred, and a single bond or -CR １ R ２ - is preferable. R １ and R ２Each of these independently represents a hydrogen atom, a C1-C10 alkyl group, a C6-C18 aryl group, or a trifluoromethyl group, with a hydrogen atom, a C1-C6 alkyl group, or a trifluoromethyl group being preferred. ３１ , R ３２ , R ４１ and R ４２ Each of these is preferably a hydrogen atom, a C1-C10 alkyl group, a C6-C18 aryl group, a fluorine atom, or a trifluoromethyl group, and more preferably a hydrogen atom, a C1-C4 alkyl group, or a trifluoromethyl group. ５１ and R ５２ Each of these is preferably a hydrogen atom, a C1-C10 alkyl group, a C6-C18 aryl group, a fluorine atom, or a trifluoromethyl group, and more preferably a hydrogen atom, a C1-C4 alkyl group, or a trifluoromethyl group.

[0040] <<*>> In formula (Y1-1), the * is bonded by a single bond to the nitrogen atom in the substructure shown in formula (A-1a) or the nitrogen atom in the substructure shown in formula (A-1b) without the use of a linking group, which is also a preferred embodiment of the present invention.

[0041] <<Ay １３ >> In formula (Y1-2), Ay １１ and Ay １２ Each of these groups is preferably a polymerizable group represented by formula (M-1) or formula (M-2) above, and more preferably the group represented by formula (M-1). Also, in formula (Y1-2), Ay １１ and Ay １２ Preferably, each of these is an independent group represented by formula (Z-1) described later.

[0042] <<m3>> In formula (Y1-2), m3 is preferably 1 or 2, and more preferably 1.

[0043] <<R ２３ >> In formula (Y1-2), R ２３The group is preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a fluorine atom, or a trifluoromethyl group, and more preferably an alkyl group having 1 to 4 carbon atoms, a phenyl group, a fluorine atom, or a trifluoromethyl group.

[0044] <<n3>> In formula (Y1-2), n3 is preferably an integer between 0 and 2, and more preferably 0 or 1.

[0045] <<*>> In formula (Y1-2), the * is bonded by a single bond to the nitrogen atom in the substructure shown in formula (A-1a) or the substructure shown in formula (A-1b) without the use of a linking group, which is also one of the preferred embodiments of the present invention.

[0046] << Other Y １ >> Furthermore, in the substructure shown by formula (A-1a) and the substructure shown by formula (A-1b), Y １ It is also preferable that the structure is one other than those described in formulas (Y1-1) and (Y1-2). For example, Y １ This may be the structure described in paragraphs 0042 to 0053 of Japanese Patent Publication No. 2023-003421, the structure described in paragraphs 0075 to 0085 of Japanese Patent Publication No. 2023-166413, the structure described in paragraphs 0110 to 0115 of International Publication No. 2022019255, etc. Also, Y １ It is preferable that the structure does not contain an imide structure.

[0047] Y １ The structure is also preferably one of the following formulas (Yp-1) to (Yp-16). * indicates a bonding site with the nitrogen atom.

[0048] In equations (Yp-1) to (Yp-16), L either does not exist independently, or represents a single bond, -CH=CH-, or -CH ２ CH ２ -ien-CH ２ -, -C (CH ３ ) ２ -, or -C (CF ３ ) ２ - represents R １０ ~R １５Each of these independently represents one of the following: an alkyl group, an aryl group, a fluoroalkyl group, a fluoroaryl group, an alkoxy group, an aryloxy group, a hydroxyl group, a carboxyl group, or a halogen atom. １６ and R １７ Each of the following independently represents a hydrogen atom, an alkyl group, or an aryl group. a to f each independently represent an integer from 0 to 3. n represents an integer from 1 to 12. R １０ ~R １５ The replacement position is not specifically designated.

[0049] In formulas (Yp-1) to (Yp-16), Y １ or Y ２ represents a single bond or a divalent linking group, and is either a single bond or -C(Rx) ２ - (Rx represents a hydrogen atom or substituent. If Rx is a substituent, they may be linked together to form a ring), -O-, -S (=O) ２ -, -C(=O), -S-, -NR Ｎ -, alkylene group, cycloalkylene group, alkenylene group, alkylylene group, arylene group, heteroarylene group, -C(=O)O-, -C(=O)NH-, or combinations thereof are preferred, single bond or -C(Rx) ２ - is more preferable. When Rx represents a substituent, specific examples include an alkyl group, an alkyl group which may be substituted with a fluorine atom, or a fluorenyl group. Ｎ represents a hydrogen atom or an organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.

[0050] Linking group Y １ or Y ２ Furthermore, it is even more preferable that the linking group is a divalent group represented by the following general formula (Y1-1) in that it exhibits excellent mechanical strength. In formula (Y1-1), each group T １ , T ２ , P １ , P ２ , P ３ Q １ Q ２ n, m, p, and q are equivalent to the equations (X1-1) described later.

[0051] Linking group Y １ or Y ２ More specifically, the following structure is preferred because it can achieve both high strength and high elongation.

[0052] Examples of commercially available diamine monomers mentioned above include aromatic diamines such as 4,4'-diaminodiphenylsulfone, 1,5-naphthalenediamine, 4,4'-diaminostilbene-2,2'-disulfonic acid, m-xylylenediamine, p-xylylenediamine, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenylsulfone, 4,4'-methylenebis(2,6-diethylaniline), 1,3-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-Methylenebis(2-chloroaniline), 1,4-Bis[2-(4-aminophenyl)-2-propyl]benzene, 4,4'-Diamino-2,2'-Biphenyldisulfonic acid, 1,4-Phenylenediamine, o-Tolidine, m-Tolidine, 1,3-Phenylenediamine, 4-Aminobenzylamine, 2,2-Bis[4-(4-aminophenoxy)phenyl]propane, 2,5-Dimethyl-1,4-Phenylene Diamine, 9,9-bis(4-aminophenyl)fluorene, o-dianisidine, 2,2-bis(4-aminophenyl)hexafluoropropane, 2,2'-bis(trifluoromethyl)benzidine, 2,7-diaminofluorene, 3,4'-diaminodiphenylmethane, 3,3',5,5'-tetramethylbenzidine, 9,9-bis(4-amino-3-methylphenyl)fluorene, bis(3-amino-4-hydrox bis(4-aminophenoxy)sulfone, 3-aminobenzylamine, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(3-aminophenoxy)benzene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 4,4'-bis(4-aminophenoxy)biphenyl, 1,1-bis(4-aminophenyl)cyclohexane, 4,6-diaminoresorcinol, 3,4'-diaminodiphenyl ether, 4,4'-ethylenedianiline, 2,3,5,6-tetramethyl-1,4-phenylenediamine, 2,2-bis(3-amino-4-hydroxyphenyl)propane, 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene, 2,6-diaminoanthraquinone, bis(2-aminophenyl)sulfide, 1,3-Bis[2-(4-aminophenyl)-2-propyl]benzene, 1,3-Bis(4-aminophenoxy)benzene, Bis[4-(3-aminophenoxy)phenyl]sulfone, Bis[4-(4-aminophenoxy)phenyl]sulfone, 4,4'-Methylenebis(2-ethyl-6-methylaniline), Bis(4-aminophenyl)sulfide, 3,7-Diamino-2,8-Dimethyldibenzothiophenesulfone, 4,4'-Diamino-3,3'-Dimethyldiphenylmethane, 2,4,5,6-Tetrafluoro-1,3-Phenylenediamine, 4,4''-Diamino-p Examples include terphenyl, 3,3'-dimethylnaphthidine, 4,4'-diaminobenzophenone, 4,4'-diaminooctafluorobiphenyl, 3,3'-diaminobenzophenone, 3,3'-diaminodiphenylmethane, 3,6-diaminocarbazole, 9,9-bis(4-amino-3-fluorophenyl)fluorene, 9,9-bis(4-amino-3-chlorophenyl)fluorene, 4,4'-diamino-2,2'-dimethylbibenzyl, 9,9-bis(4-aminophenyl)fluorene, and 2,3,5,6-tetrafluoro-1,4-phenylenediamine. Suitable aliphatic diamines include, for example, bicyclo[2.2.1]heptanedimethanamine (isomer mixture), 4,4'-methylenebis(cyclohexylamine) (isomer mixture), 4,4'-methylenebis(2-methylcyclohexylamine) (isomer mixture), isophoronediamine (cis-, trans- mixture), 1,3-bis(aminomethyl)cyclohexane (cis-, trans- mixture), 1,4-bis(aminomethyl)cyclohexane (cis-, trans- mixture), 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-cyclohexanediamine (cis-, trans- mixture), and 1,4-cyclohexanediamine (cis-, trans- mixture).

[0053] Other diamines that can be used include BPF-AN (manufactured by JFE Chemical Co., Ltd.) and pyridazine-based sulfur-containing diamine APP (manufactured by Nippon Materials Technology Co., Ltd.), which can be suitably used to enhance the transparency of polyimide or amical resins.

[0054] In addition, the diamines described in JP-A No. 2023-166413 and WO 2022 / 019255 can be preferably used.

[0055] The specific resin preferably contains two types of the following formula (A-2a1) and the following formula (A-2b1) as a partial structure represented by the formula (A-1a). In the formula (A-2a1), Ya ２ represents a structure represented by the following formula (Y-1), Ay ２ represents a group represented by the following formula (Z-1), and n2 is an integer of 1 or 2. In the formula (A-2b1), Yb ２ represents a structure represented by the following formula (Y-2). In the formula (Y-1), Ar １ represents an aromatic group having 6 to 10 carbon atoms which may have a substituent, L １ represents a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR [[ID=3I]] ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ - or -CR ４ ２ represents, Y １ represents an aromatic group having 6 to 30 carbon atoms which may have a substituent, a represents an integer of 0 to 3, and * represents a bonding site with a nitrogen atom. In the formula (A-2a1), when Ya ２ is represented by the following formula (Y-3), at least one of Ar １ and Y １ has a bonding site with Ay ２ as a substituent. In the formula (Y-2), Ar ２ represents an aromatic group having 6 to 10 carbon atoms which may have a substituent, L ２ represents a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ - or -NR ３ (C=O)NR ２ - indicates Y ２ represents an aromatic group having 6 to 30 carbon atoms, which may have substituents, b represents an integer from 0 to 3, and * represents a bonding site with a nitrogen atom. In formula (Z-1), Lx １ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates Lx ２ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates R １ R represents a hydrogen atom or a monovalent organic group. ２ R represents a hydrogen atom or a monovalent organic group. ３R represents a hydrogen atom or a monovalent organic group. ４ R represents a hydrogen atom or a monovalent organic group. ５ represents a monovalent organic group, La represents the group shown in the following formula (La-1), Lb represents a C1-C12 r4+1 valent hydrocarbon group, a group consisting of any or a combination of the above formulas (Lb-1) to (Lb-3), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r1 represents 0 or 1, r2 represents 0 or 1, r3 represents an integer from 0 to 5, r4 represents an integer from 1 to 10, and * represents Ar of formula (Y-1). １ or Y １ This shows the binding site. In formula (La-1), Ra １ , Ra ２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and * represents Lx １ The wavy line indicates the connection point with Lx ２ The binding sites with either Lb or A are shown, respectively.

[0056] <<Ya ２ >> In equation (A-2a1), Ya ２ This shows the structure represented by equation (Y-1). In equation (A-2a1), Ya ２ It is preferable that this is the above formula (Y1-1) or the above formula (Y1-2).

[0057] In formula (Y-1), Ar １ It is preferable that the substituent is a C6 aromatic group which may have substituents. Examples of substituents include the group represented by formula (Z-1), alkyl groups, aryl groups, alkoxy groups, aryloxy groups, etc., with the group represented by formula (Z-1) being preferred. Furthermore, an embodiment having only the group represented by formula (Z-1) as a substituent is also one of the preferred embodiments of the present invention.

[0058] In formula (Y-1), L １ is a single bond or -CR ４ ２ - is preferable. L １ In R １ A hydrogen atom or an alkyl group is preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred. １ In R２ A hydrogen atom or an alkyl group is preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred. １ In R ３ A hydrogen atom or an alkyl group is preferred, a hydrogen atom or a methyl group is more preferred, and a hydrogen atom is even more preferred. １ In R ４ Each of these is independently preferably a hydrogen atom, an alkyl group, an aryl group, a halogen atom, or a trifluoromethyl group, and more preferably a methyl group.

[0059] In equation (Y-1), Y １ It is preferable that is a C6 aromatic group which may have substituents. Examples of substituents include the group represented by formula (Z-1), alkyl groups, aryl groups, alkoxy groups, aryloxy groups, etc.

[0060] In formula (Y-1), Ar １ and Y １ At least one of them is Ay as a substituent. ２ It has a bonding site with the above. It is also a preferred embodiment of the present invention that both have the above bonding site. １ Ay in ２ The number of bonding sites is preferably 1 or 2, and more preferably 1. １ Ay in ２ The number of bonding sites is preferably 1 or 2, and more preferably 1.

[0061] In formula (Y-1), a represents an integer from 0 to 3, preferably 0 or 1, and more preferably 1.

[0062] <<Ay ２ >> In formula (A-2a1), Ay ２ It is preferable that this is the above formula (M-1) or (M-2).

[0063] In formula (Z-1), Lx １ is -O-, -(C=O)O-, -(C=O)NR ２ -, -O(C=O)NR ２It is preferable that it be -, and more preferably -O- or -(C=O)O-. In particular, -O- is preferred from the viewpoint of reducing the dielectric loss tangent. L Ｘ１ In R １ ~R ４ A preferred embodiment is L １ In R １ ~R ４ This is similar to the preferred embodiment of L. Ｘ１ In R ５ The group is preferably an alkyl group or an aryl group, and more preferably an alkyl group.

[0064] In formula (Z-1), La represents the group shown in formula (La-1), and in formula (La-1), Ra １ , Ra ２ Each of these is preferably a hydrogen atom, a C1-C10 alkyl group, or a phenyl group, more preferably a hydrogen atom or a C1-C10 alkyl group, and even more preferably a methyl group. １ and Ra ２ Another preferred embodiment of the present invention is one in which one of the atoms is a hydrogen atom and the other is an alkyl group having 1 to 10 carbon atoms (preferably a methyl group).

[0065] In formula (Z-1), r1 is 1 or 0, and is preferably 0.

[0066] In formula (Z-1), Lx ２ ha -O-, -(C=O)O-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ４ ) - CH ２ It is preferable that it be -, and more preferably that it be -O-.

[0067] In formula (Z-1), r2 is 1 or 0, and if Lb is one of formulas (Lb-1) to (Lb-3), or a combination thereof, it is preferably 1.

[0068] In formula (Z-1), when Lb is a C1-C12 r4+1 valent hydrocarbon group, Lb is preferably a C1-C12 r4+1 valent saturated aliphatic hydrocarbon group, and more preferably a C2-C6 r4+1 valent saturated aliphatic hydrocarbon group. For example, when r4=1, Lb is preferably a C1-C12 alkylene group, and more preferably an alkylene group. The hydrocarbon group in Lb, or the hydrogen atom in the saturated aliphatic hydrocarbon group, may be substituted with known substituents.

[0069] Furthermore, Lb is preferably a group represented by formulas (Lb-1) to (Lb-3), or by a combination thereof, and is also preferably a group represented by formula (Lb-1), formula (Lb-2), or by a combination thereof. Preferred embodiments of formulas (Lb-1) to (Lb-3) are as described above.

[0070] In formula (Z-1), r3 represents an integer from 0 to 5, preferably an integer from 0 to 3, and preferably 0, 1, or 2. An embodiment in which r3 is from 1 to 5 and Lb includes any of formulas (Lb-1) to (Lb-3) is also one of the preferred embodiments of the present invention. The structures represented by formulas (Lb-1) to (Lb-3) are thought to be easily decomposed by heating. Therefore, for example, when heating (for example, heating to 180°C or higher) is performed during the formation of the cured product, the structures represented by formulas (Lb-1) to (Lb-3) are decomposed, making it easier for the resin to orient in the cured product, and it is presumed that the CTE is likely to decrease.

[0071] In formula (Z-1), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, and is preferably a group having an ethylenically unsaturated bond. Preferred groups having an ethylenically unsaturated bond include (meth)acryloyl groups, vinylphenyl groups, or maleimide groups. Other known groups having an ethylenically unsaturated bond, such as vinyl groups and allyl groups, may also be used.

[0072] In formula (Z-1), r4 is preferably an integer between 1 and 6, more preferably an integer between 1 and 3, and even more preferably 1 or 2.

[0073] In equation (Z-1), * represents Ar in equation (Y-1). １ or Y １ It is preferable that the bonding site is with Ar １ or Y １ It is preferable that the aromatic group and the linking group are bonded without a linking group in between.

[0074] <<n2>> In equation (A-2a1), n2 is an integer of 1 or 2. The embodiment in which n2 is 2 is also one of the preferred embodiments of the present invention.

[0075] In formula (Y-2), Ar ２ , L ２ , Y ２ A preferred embodiment of b is Ay ２ Except for not having a bonding site with, Ar in formula (Y-1) １ , L １ , Y １ The same applies to the preferred embodiment of (a), respectively.

[0076] [Substructure represented by formula (A-1b)] -X １ - In formula (A-1b), X １ X represents a cyclobutane ring. The molar amount of trans-conformed cyclobutane rings relative to the total molar amount of cyclobutane rings contained in the resin is preferably 80% or more, and particularly preferably 95% or more. There is no particular upper limit, but it is preferably 99% or less. In addition, in the total cyclobutane rings represented by X1 in formula (A-1b), the molar amount of trans-conformed cyclobutane rings is preferably 80% or more, and particularly preferably 95% or more. There is no particular upper limit, but it is preferably 99% or less.

[0077] -Y １ - In formula (A-1b), Y １ This indicates a divalent organic group. Y １ Preferably, it includes at least the structure represented by the above formula (Y1-1) or the above formula (Y1-2). However, in formula (A-1b), Y １ In the embodiment where m1, m2 in formula (Y1-1) and m3 in formula (Y1-2) are 0, this is also one of the preferred embodiments of the present invention.

[0078] -R １ , R ２ - In formula (A-1b), R １ , R ２ Each of these is preferably a monovalent organic group. １ or Ax ２ If the group is a monovalent organic group, it is preferable that the monovalent organic group is a group represented by the following formula (AX-1). In formula (AX-1), A ＡＸ is -O- or -NR Ｚ - and R Ｚ R is a hydrogen atom or a monovalent organic group. ＡＸ It is a monovalent organic group.

[0079] <<A ＡＸ >> In formula (AX-1), A ＡＸ It is preferable that is -O-. In formula (AX-1), A ＡＸ ga-NR Ｚ - If R Ｚ It is preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom.

[0080] <<A ＡＸ >> In formula (AX-1), R ＡＸ It is preferable that it contains a linear or branched alkyl group, a cyclic alkyl group, an aromatic group, or a polyalkylene oxy group. Also, Ax １ and Ax ２ At least one of them is R ＡＸ It is preferable that one contains polymerizable groups, and more preferably that both contain polymerizable groups. Ax １ and Ax ２ At least one of them is R ＡＸIt is also preferable that the polyimide precursor contains two or more polymerizable groups. The polymerizable groups are groups that can undergo crosslinking reactions by the action of heat, radicals, etc., and radical polymerizable groups are preferred. Specific examples of polymerizable groups include groups having an ethylenically unsaturated bond, alkoxymethyl groups, hydroxymethyl groups, acyloxymethyl groups, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, and amino groups. As radical polymerizable groups in the polyimide precursor, groups having an ethylenically unsaturated bond are preferred. Examples of groups having an ethylenically unsaturated bond include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (for example, vinylphenyl groups), (meth)acrylamide groups, (meth)acryloyloxy groups, and groups represented by the following formula (III), with groups represented by the following formula (III) being preferred.

[0081]

[0082] In equation (III), R ２００ R represents a hydrogen atom, a methyl group, an ethyl group, or a methylol group, with a hydrogen atom or a methyl group being preferred. In formula (III), * represents a bonding site with other structures. In formula (III), R ２０１ This is an alkylene group having 2 to 12 carbon atoms, -CH ２ CH(OH)CH ２ - represents a cycloalkylene group or a polyalkylene oxy group. Preferred R ２０１ Examples include alkylene groups such as ethylene, propylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, and dodecamethylene, as well as 1,2-butanediyl, 1,3-butanediyl, and -CH ２ CH(OH)CH ２ -Polyalkylene oxy groups are examples, including alkylene groups such as ethylene groups and propylene groups, and -CH ２ CH(OH)CH ２-, cyclohexyl groups, polyalkylene oxy groups are more preferred, alkylene groups such as ethylene groups and propylene groups, or polyalkylene oxy groups are even more preferred. In the present invention, a polyalkylene oxy group refers to a group in which two or more alkylene oxy groups are directly bonded. The alkylene groups in the multiple alkylene oxy groups contained in the polyalkylene oxy group may be the same or different. When the polyalkylene oxy group contains multiple types of alkylene oxy groups with different alkylene groups, the arrangement of the alkylene oxy groups in the polyalkylene oxy group may be random, have blocks, or have patterns such as alternating arrangements. The number of carbon atoms in the alkylene group (including the number of carbon atoms of the substituents if the alkylene group has substituents) is preferably 2 or more, more preferably 2 to 10, even more preferably 2 to 6, even more preferably 2 to 5, even more preferably 2 to 4, even more preferably 2 or 3, and particularly preferably 2. The alkylene group may also have substituents. Preferred substituents include alkyl groups, aryl groups, halogen atoms, etc. The number of alkylene oxy groups contained in the polyalkylene oxy group (number of repeating polyalkylene oxy groups) is preferably 2 to 20, more preferably 2 to 10, and even more preferably 2 to 6. From the viewpoint of solvent solubility and solvent resistance, the polyalkylene oxy group is preferably a polyethylene oxy group, a polypropylene oxy group, a polytrimethylene oxy group, a polytetramethylene oxy group, or a group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, more preferably a polyethylene oxy group or a polypropylene oxy group, and even more preferably a polyethylene oxy group. In the group in which multiple ethylene oxy groups and multiple propylene oxy groups are bonded, the ethylene oxy groups and propylene oxy groups may be arranged randomly, in blocks, or in alternating patterns. The preferred configurations for the number of repeating ethylene oxy groups in these groups are as described above.

[0083] In equation (AX-1), RＡＸ If is a hydrogen atom, it may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. An example of such a tertiary amine compound having an ethylenically unsaturated bond is N,N-dimethylaminopropyl methacrylate.

[0084] In equation (AX-1), R ＡＸ A structure represented by a linear or branched alkyl group, and R ＡＸ Embodiments that include both structures represented by groups having ethylenically unsaturated bonds are particularly preferred embodiments.

[0085] Among these, in equation (A-1b), R １ and R ２ It is preferable that the structure is represented by the following formula (R-1).

[0086] It is preferable that the substructure represented by formula (A-1b) includes two types: the following formula (A-2a2) and the following formula (A-2b2).

[0087] In formula (A-2a2), Ya ２ This shows a structure represented by the following formula (Y-3), and R ５１ , R ５２ Ay ３ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, or the following formula (Z-2). n3 is an integer from 0 to 3, and when n3 = 0, R ５１ , R ５２ At least one of them represents a group represented by formula (Z-2). In formula (A-2b2), Yb ２ R indicates a divalent organic group, ５１ , R ５２ represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group, or the following formula (Z-2). In formula (Y-3), Ar ３ L represents an aromatic group having 6 to 10 carbon atoms, which may have substituents. １ The bond is a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ - or -NR ３ (C=O)NR ２ - indicates Y ３ represents an aromatic group having 6 to 30 carbon atoms, which may have substituents, a represents an integer from 0 to 3, and * represents a bonding site with a nitrogen atom. In formula (A-2a2), Ya ２ If it is expressed by the following formula (Y-3), Ar ３ and Y ３ At least one of them is Ay as a substituent. ３ It has a bonding site with. In formula (Z-2), Lx １ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates Lx ２ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH２ - indicates R １ R represents a hydrogen atom or a monovalent organic group. ２ R represents a hydrogen atom or a monovalent organic group. ３ R represents a hydrogen atom or a monovalent organic group. ４ R represents a hydrogen atom or a monovalent organic group. ５ represents a monovalent organic group, La represents the group shown in the following formula (La-1), Lb represents a C1-C12 r4+1 valent hydrocarbon group, a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r1 represents 0 or 1, r2 represents 0 or 1, r3 represents an integer from 0 to 5, r4 represents an integer from 1 to 10, and * represents Ar of formula (Y-3). ３ or Y ３ This shows the binding site. In formula (La-1), Ra １ , Ra ２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and * represents Lx １ The wavy line indicates the connection point with Lx ２ The binding sites with either Lb or A are shown, respectively. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z each independently represent an integer from 1 to 30.

[0088] In formula (A-2a2), Ya ２ and Ay ３ A preferred embodiment is Ya in formula (A-2a1) ２ and Ay ２ This is similar to a preferred embodiment. In formula (A-2a2), R ５１ , R ５２ A preferred embodiment is R in formula (A-1b). １ , R ２ This is similar to the preferred embodiment.

[0089] <<Ya ２ >> In formula (A-2a2), Ya ２ It is preferable that is formula (Y1-1) or formula (Y1-2).

[0090] <<Ay ３ >> In formula (A-2a2), Ay ３ It is preferable that the formula is (M-1) or (M-2).

[0091] In formula (A-2b2), Yb ２ A preferred embodiment is Yb in formula (A-2a2). ２ This is similar to a preferred embodiment. In formula (A-2b2), R ５１ , R ５２ A preferred embodiment is R in formula (A-1b). １ , R ２ This is similar to the preferred embodiment.

[0092] [Content of substructures] The total content of the substructure represented by formula (A-1a) or formula (A-1b) relative to the total mass of the specific resin is preferably 50 mol% or more, more preferably 70 mol% or more, even more preferably 80% or more, and particularly preferably 90% by mass or more. The upper limit of the above content is not particularly limited and may be 100% by mass. Furthermore, if the specific resin contains the substructure represented by formula (A-1a), it may contain two or more substructures represented by formula (A-1a) with different structures. In that case, it is preferable that the total amount is within the above range. If the specific resin contains the substructure represented by formula (A-1b), it may contain two or more substructures represented by formula (A-1b) with different structures. In that case, it is preferable that the total amount is within the above range.

[0093] [Other substructures] The specified resin may have at least one substructure selected from the group consisting of the substructure represented by formula (A2-1a) and the substructure represented by formula (A2-1b), and may include these substructures as repeating units. The substructure represented by formula (A2-1a) and the substructure represented by formula (A2-1b) are substructures that do not fall under either of the substructures represented by formula (A-1a) and the substructures represented by formula (A-1b) described above. In formula (A2-1a), X ２ This indicates a tetravalent organic group, Y １ represents a divalent organic group. In formula (A2-1b), X２ This indicates a tetravalent organic group, Ax １ and Ax ２ Each independently represents a hydrogen atom or a monovalent organic group, Y １ This indicates a divalent organic group.

[0094] -X ２ - In formula (A2-1a) and formula (A2-1b), X ２ The structure is preferably derived from an acid anhydride monomer, but is not limited thereto. The acid anhydride monomer is not particularly limited as long as it has two cyclic acid anhydride groups in one molecule. It may be an aromatic acid anhydride, an aliphatic acid anhydride, or a mixture thereof.

[0095] X ２ The following formulas (Xp-1) to (Xp-23) are preferably used. In the following formulas (Xp-1) to (Xp-23), *1 represents the bonding site with the carbonyl group indicated as *1 in the following formula (PX-1) or formula (PX-2), and *2 represents the bonding site with the carbonyl group indicated as *2 in the following formula (PX-1) or formula (PX-2). The following formulas (PX-1) and (PX-2) are formulas (A2-1a) and (A2-1b) respectively, to which the symbols *1 and *2 have been added for convenience.

[0096] In equations (Xp-1) to (Xp-23), L either does not exist independently, or is a single bond, -CH=CH-, -CH ２ CH ２ -ien-CH ２ -, -C (CH ３ ) ２ -, or -C (CF ３ ) ２ - represents R １ and R ２ Each of these independently represents a hydrogen atom or a substituent, R １ and R ２ They may bond to form a ring structure, and the formed ring may be an aromatic ring, R １ and R ２R can also form a ring to create a benzene ring. If multiple L molecules are present in one molecule, they may be the same or different. ３ , R ４ , R ５ , R ６ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and adjacent R ３ ~R ６ The divalent organic groups may be linked to form a ring. ７ , R ８ n1 represents one of the following: alkyl group, aryl group, fluoroalkyl group, fluoroaryl group, alkoxy group, aryloxy group, hydroxyl group, carboxyl group, or halogen atom. n1 and n2 each independently represent integers from 0 to 4. If stereogeometric isomers exist, the distinction between cis / trans and endo / exo is not particularly limited.

[0097] In formulas (Xp-1) to (Xp-23), X １ ~X ４ represents a single bond or a divalent linking group, and is either a single bond or -C(Rx)2- (where Rx represents a hydrogen atom or a substituent; if Rx is a substituent, they may be linked together to form a ring), -O-, or -S(=O). ２ -, -C(=O), -S-, -NR Ｎ -, alkylene group, cycloalkylene group, alkenylene group, alkylylene group, arylene group, heteroarylene group, -C(=O)O-, -C(=O)NH-, or combinations thereof are preferred, single bond or -C(Rx) ２ - is more preferable. When Rx represents a substituent, specific examples include an alkyl group, an alkyl group which may be substituted with a fluorine atom, or a fluorenyl group. Ｎ represents a hydrogen atom or an organic group, preferably a hydrogen atom, an alkyl group, or an aryl group, and more preferably a hydrogen atom or an alkyl group.

[0098] Linking group X １ ~X ４ Furthermore, it is even more preferable that the linking group is a divalent group represented by the following general formula (X1-1) in that it exhibits excellent mechanical strength. In equation (X1-1), n ​​and m each independently represent either 0 or 1. １ , T ２ Each of these independently represents a single bond, -O-, -S-, or -NR-. Here, R represents a hydrogen atom, an alkyl group, or an aryl group. P １ , P ２ , and, P ３ Each of these independently represents one of the following: an aromatic group having 6 to 12 carbon atoms, a heterocyclic group having 5 to 12 carbon atoms, an aliphatic group having 1 to 12 carbon atoms, or an alicyclic group having 4 to 12 carbon atoms. １ , P ２ and P ３ Each of these groups may have further substituents, such as alkyl groups, fluoroalkyl groups, aryl groups, alkoxy groups, aryloxy groups, hydroxyl groups, carboxyl groups, and halogen atoms. The positions of these substitutions are not particularly limited. Q １ and Q ２ Each is independently a single bond, -C(R) ２ -, -O-, -S-, -NR-, -C(=O)O-, -C(=O)NR-, -C(=O)-, -OC(=O)O-, -OC(=O)NR-, -NRC(=O)NR-, -S(=O)-, -S(=O) ２ This represents a divalent organic group consisting of one or a combination thereof. Here, R independently represents a hydrogen atom, an alkyl group, a fluoroalkyl group, or an aryl group, and Rs may be bonded to each other to form a ring. p and q independently represent 0 or 1.

[0099] Linking group X １ ~X ４ More specifically, the following structure is preferred because it can achieve both high strength and high elongation.

[0100] Commercially available acid anhydride monomers include, for example, pyromellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,4,9,10-perylenetetracarboxylic dianhydride, 4-chloroformylphthalic anhydride, trimellitic anhydride, tetrachlorophthalic anhydride, phthalic anhydride, naphthalene-1,4,5,8-tetracarboxylic dianhydride, 4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 4,4'-oxydiphthalic anhydride, 4,4'-(4,4'-isopropylidene diphenoxy)diphthalic anhydride, 4,4'-biphthalic anhydride, tetrabromophthalic anhydride, 3,4'-oxydiphthalic anhydride, 4-(1-propynyl)phthalic anhydride, 4,4'-(ethyn-1,2-diyl)diphthalic anhydride, bis(1,3-dioxo-1,3-dihydroisobenzofuran-5-carboxylic acid)1,4-phenylene, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride Examples include (sublimation purified products), pyromellitic anhydride (sublimation purified products), 4-phenylethynylphthalic anhydride, tetrafluorophthalic anhydride, 4,4'-sulfonyl diphthalic anhydride, 4-ethynylphthalic anhydride, and diphenyl-2,3,3',4'-tetracarboxylic dianhydride.Examples of aliphatic dianhydrides include bicyclo[2.2.2]octo-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, ethylenediaminetetraacetic acid dianhydride, dicyclohexyl-3,4,3',4'-tetracarboxylic acid dianhydride, meso-butane-1,2,3,4-tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, and 4-(2,5-dioxotetrahydrofuran-3 The following can be suitably used: -yl)-1,2,3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride, octahydrobiphenylene-4a,8b:4b,8a-tetracarboxylic acid dianhydride, 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 3-(carboxymethyl)-1,2,4-cyclopentanetricarboxylic acid 1,4:2,3-dianhydride.

[0101] Other acid anhydrides that can be used include CpODA (manufactured by ENEOS), BzDA (manufactured by ENEOS), BzDAxx (manufactured by ENEOS), BNBDA (manufactured by ENEOS), TMPBP-TME (manufactured by Honshu Chemical Co., Ltd.), BPZ-TME (manufactured by Honshu Chemical Co., Ltd.), BPF-PA (manufactured by JFE Chemical Co., Ltd.), and 5,5′-[p-phenylenebis(oxycarbonyl)]diphthalic anhydride (trade name: TAHQ, manufactured by Manac Co., Ltd.), which can be suitably used to enhance the transparency of polyimide or amical resin.

[0102] In addition, acid anhydrides described in International Publication No. 2022 / 019253, Japanese Patent Publication No. 2023-166413, and International Publication No. 2022 / 019255 can be suitably used.

[0103] In formula (A2-1a) and formula (A2-1b), X ２ The group is preferably represented by formula (5) or formula (6) below. In formula (5) or formula (6), * independently represents a bonding site with another structure. In formula (5), R １１２The linking group is a single bond or a divalent linking group, and may be a single bond or a carbon-1 to carbon-10 aliphatic hydrocarbon group, -O-, -CO-, -S-, -SO- which may be substituted with a fluorine atom. ２ Preferably, the group is selected from -, -NHCO-, and combinations thereof, and is a C1- to C3 alkylene group, -O-, -CO-, -S-, and -SO- which may be single-bonded or substituted with a fluorine atom. ２ - More preferably, the group is selected from -CH ２ -, -C(CF ３ ) ２ -, -C(CH ３ ) ２ -, -O-, -CO-, -S-, and -SO ２ It is even more preferable that the group is a divalent group selected from the group consisting of -.

[0104] X ２ It is preferable that it does not have a cyclobutane ring.

[0105] Furthermore, from the standpoint of resin transparency, X ２ It is also preferable that the structure includes an alicyclic structure. Structures represented by the following formulas (X2-1) or (X2-2) are also suitably used as structures including an alicyclic acid structure. In formula (X2-1), R Ｘ２１ , R Ｘ２２ , R Ｘ２３ Each of the following is independently a hydrogen atom, a C1-C5 alkyl group, or a fluorine atom, n is an integer from 0 to 12, and * is the bonding site to the carbonyl group. In formula (X2-2), A represents a single bond or a divalent linking group, each of the following is independently a hydrogen atom, a C1-C5 alkyl group, or a C2-C5 alkenyl group, and * is the bonding site to the carbonyl group.

[0106] In formula (X2-1), R Ｘ２１ , R Ｘ２２ , R Ｘ２３ Each of these is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom. In formula (X2-1), n ​​is preferably 1 to 5, and more preferably 2 or 3.

[0107] In formula (X2-2), A is preferably a single bond or a phenylene group, and more preferably a 1,4-phenylene group.

[0108] Other, X ２ From the perspective of possessing both flexibility and linearity, it is also preferable to use a structure represented by the following formula (X2-3). In formula (X2-3), Z １１ and Z １２ Each of the symbols independently represents an organic group, a1 and a2 independently represent 1 or 0, and L independently represents a single bond, -O-, -S-, -S=O-, and -S(=O). ２ -, -C=O-, -CRR-, -CRR-CRR-, or -CR=CR-, where R independently represents an alkyl group, an aryl group, a halogen atom, an alkoxy group, or a trifluoromethyl group, R Ｓ Each of these independently represents an alkyl group, an aryl group, a halogen atom, an OH group, a COOH group, an alkoxy group, or a trifluoromethyl group, R Ｓ The elements may bond to each other to form a ring, the ring may be an aromatic ring, m represents an integer from 0 to 4, b represents an integer of 0 or 1, and * represents the bonding site with the carbonyl group.

[0109] In formula (X2-3), Z １１ and Z １２Each of these independently represents an organic group, preferably a hydrocarbon group, more preferably a group obtained by removing three hydrogen atoms from an aromatic hydrocarbon ring, or more preferably a group obtained by removing three hydrogen atoms from an aliphatic hydrocarbon group. From the viewpoint of solvent solubility and developability of the resin, a group obtained by removing three hydrogen atoms from an aromatic hydrocarbon ring is preferred, and from the viewpoint of resolution and ultraviolet light transmittance, a group obtained by removing three hydrogen atoms from an aliphatic hydrocarbon group is preferred. As the above aromatic hydrocarbon ring, an aromatic hydrocarbon ring having 6 to 18 carbon atoms is preferred, an aromatic hydrocarbon ring having 6 to 10 carbon atoms is more preferred, and a benzene ring is even more preferred. As the above aliphatic hydrocarbon group, it may be a chain-like aliphatic hydrocarbon group or an aliphatic hydrocarbon ring. As the above chain-like aliphatic hydrocarbon group, it may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. As the above chain-like aliphatic hydrocarbon group, the number of carbon atoms is preferably 2 to 10, and more preferably 3 to 6. As the above aliphatic hydrocarbon ring, it may be monocyclic or polycyclic. If polycyclic, it may be a fused ring, a crosslinked ring, or a spiro ring, but a crosslinked ring is preferred. The number of carbon atoms in the aliphatic hydrocarbon ring is preferably 4 to 20, more preferably 5 to 12, and even more preferably 6 to 10. In formula (X2-3), a1 and a2 are preferably 1. In formula (X2-3), L is preferably a single bond, -O-, -C=O-, -CRR-, -CRR-CRR-, or -CR=CR-, independently. R is preferably an alkyl group or trifluoromethyl, independently. In formula (X2-3), R Ｓ Each of these is preferably an alkyl group, a halogen atom, an OH group, a COOH group, an alkoxy group, or a trifluoromethyl group. In addition, in formulas (A2-1a) and (A2-1b), X ２ Preferred embodiments include the structure described in paragraphs 0055 to 0057 of Japanese Patent Publication No. 2023-003421, the structure described in paragraphs 0099 to 0108 of Japanese Patent Publication No. 2023-166413, and the structure described in paragraphs 0065 to 0080 of International Publication No. 2022 / 019255.

[0110] In formula (A2-1a) and formula (A2-1b), Y １A preferred embodiment is Y in formula (A-1a). １ This is similar to the preferred embodiment.

[0111] In formula (A2-1b), Ax １ and Ax ２ A preferred embodiment is R in formula (A-1b). １ and R ２ This is similar to the preferred embodiment.

[0112] The specific resin may also preferably include at least one substructure selected from the group consisting of the substructure represented by the following formulas (A-11), (A-12), (A-13), and (A-14), as a substructure represented by formula (A-1a) or (A-1b). In formula (A-11), X １１ represents a cyclobutane ring, and in formula (A-12), X １１ R represents a cyclobutane ring. １ and R ２ Each represents a hydrogen atom or a monovalent organic group, and in formula (A-13), X １１ R represents a cyclobutane ring. １ Each represents a hydrogen atom or a monovalent organic group, and in formula (A-14), X １１ R represents a cyclobutane ring. ２ Each of these represents either a hydrogen atom or a monovalent organic group.

[0113] All X contained in the resin １１ Of these, it is preferable that the molar amount of the cyclobutane ring in the trans conformation is 80% or more, and particularly preferable that it is 95-99%.

[0114] When the specific resin is a polyimide precursor, it is preferable that the molar proportion of the substructure represented by formula (A-2a1) or formula (A-2b1) is 50% or more, and particularly preferably 100% to 1000%, relative to the molar proportion of the substructure represented by formula (A2-1a). When the specific resin is polyimide, it is preferable that the molar proportion of the substructure represented by formula (A-2a2) or formula (A-2b2) is 50% or more, and particularly preferably 200% to 1000%, relative to the molar proportion of the substructure represented by formula (A2-1b).

[0115] The content of the cyclobutane ring structure in the specific resin is preferably 0.1 to 2.5 mmol / g, and particularly preferably 0.5 to 1.5 mmol / g.

[0116] [Physical Properties of Specific Resins] When the specific resin is a polyimide precursor, the weight-average molecular weight (Mw) of the polyimide precursor is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. The number-average molecular weight (Mn) of the polyimide precursor is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide precursor is preferably 1.5 or higher, more preferably 1.8 or higher, and even more preferably 2.0 or higher. There is no particular upper limit for the degree of dispersion of the molecular weight of the polyimide precursor, but for example, it is preferably 7.0 or lower, more preferably 6.5 or lower, and even more preferably 6.0 or lower. In this specification, the degree of dispersion of molecular weight is a value calculated by weight-average molecular weight / number-average molecular weight. When a resin composition contains multiple types of polyimide precursors as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one of the polyimide precursors are within the above ranges. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated by treating the multiple types of polyimide precursors as a single resin are, respectively, within the above ranges.

[0117] When the specific resin is polyimide, the weight-average molecular weight (Mw) of the polyimide is preferably 5,000 to 100,000, more preferably 10,000 to 50,000, and even more preferably 15,000 to 40,000. By setting the weight-average molecular weight to 5,000 or more, the flexural resistance of the cured film can be improved. To obtain an organic film with excellent mechanical properties (e.g., elongation at break), a weight-average molecular weight of 15,000 or more is particularly preferred. The number-average molecular weight (Mn) of the polyimide is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. The degree of dispersion of the molecular weight of the above polyimide is preferably 1.5 or more, more preferably 1.8 or more, and even more preferably 2.0 or more. There is no specific upper limit for the degree of dispersion of the molecular weight of polyimide, but for example, it is preferably 7.0 or less, more preferably 6.5 or less, and even more preferably 6.0 or less. When the resin composition contains multiple types of polyimide as a specific resin, it is preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion of at least one type of polyimide are within the above range. It is also preferable that the weight-average molecular weight, number-average molecular weight, and degree of dispersion calculated when the multiple types of polyimide are treated as a single resin are each within the above range.

[0118] When the specific resin is polyimide, the imidation rate (also called the "ring closure rate") of the polyimide is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more, from the viewpoint of the film strength, insulating properties, etc. of the resulting organic film. The upper limit of the above imidation rate is not particularly limited and may be 100% or less. Also, when the specific resin is polyimide, the content of the imide structure in the specific resin is preferably 3 mmol / g or less, and more preferably 2.5 mmol / g or less. The lower limit of the above content is not particularly limited, but for example it can be 0.5 mmol / g or more. The above imidation rate is measured by, for example, the following method.

[0119] In this invention, the imidization rate can be calculated by the following method. A specific resin is dissolved in γ-butyrolactone, diluted to a viscosity of 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. If a resin layer cannot be formed due to reasons such as low solubility of the resin in γ-butyrolactone, the solvent may be changed to another solvent. Other solvents that can be used include solvents contained in the resin composition, such as NMP. The viscosity may also be adjusted as appropriate within an adjustable range. The silicon wafer to which the obtained resin layer has been applied is dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm on the silicon wafer after film formation. Here, if only a resin solution with low viscosity can be obtained, and it is difficult to obtain a resin layer with a thickness of 15 μm, the film thickness may be changed as appropriate. For example, if the film thickness is 5 μm or more, a similar value for the imidization rate can be obtained. The above resin layer was measured using the ATR method with Nicoleti S20 (manufactured by Thermofisher), with a measurement range of 4000–700 cm. －１ The measurement will be taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１ The imidization index A of the resin is calculated by dividing the value by the peak height of the peak with the maximum peak intensity (if there are multiple peaks). The film is heated at a rate of 10°C / min under a nitrogen atmosphere and heated to 350°C for 1 hour. The imidization index B is calculated in the same manner, and the value obtained by dividing the imidization index A by the imidization index B is calculated as the imidization rate of the resin. In measuring the imidization rate, the resin to be measured for imidization rate can be obtained from the composition by, for example, the following method: A solution of 1 g of the composition and 2 g of tetrahydrofuran is added to 50 g of methanol or water and crystallized to precipitate the resin, which is then filtered. The filtrate is collected, dissolved in 3.0 g of THF (tetrahydrofuran), added to 50 g of methanol or water and crystallized, filtered, and dried at 40°C for 20 hours to obtain the resin.

[0120] When the specific resin is a polyimide precursor, the imidization rate is preferably less than 70%, more preferably 60% or less, even more preferably 50% or less, even more preferably 40% or less, and particularly preferably 30% or less, from the viewpoint of the film strength and insulating properties of the resulting organic film. The lower limit of the above imidization rate is not particularly limited and may be 0% or more, or 4% or more. The range of the imidization rate may be any combination of the above lower and upper limits, and is particularly preferably 0% or more and 30% or less.

[0121] [Acid Value] From the viewpoint of storage stability and adhesion, the acid value of the specific resin is preferably 0.066 to 0.400 mmol / g, more preferably 0.069 to 0.356 mmol / g, and even more preferably 0.071 to 0.321 mmol / g. Furthermore, the acid value of the specific resin is preferably 3.70 to 22.5 mg KOH / g, more preferably 3.85 to 20.0 mg KOH / g, and even more preferably 4.00 to 18.0 mg KOH / g. The above acid value is measured by a known method, for example, by the method described in JIS K 0070:1992.

[0122] Furthermore, from the viewpoint of adhesion, it is also preferable that the specific resin is a polyamic acid ester in which the acidic functional groups at a pH below 8.0 are less than 0.1 mg KOH / g, and the acidic functional groups at a pH of 8.0 or higher are 3.70 to 22.5 mg KOH / g when titrated under the following conditions. Conditions: 0.300 g of resin is completely dissolved in 80 mL of NMP, then 5 mL of water is mixed in, and the mixture is titrated with a 0.01 mol / L NaOH aqueous solution. Whether or not it is completely dissolved can be confirmed by visual inspection by checking for the absence of residual material. If the above amount of resin does not completely dissolve in NMP, the amount of resin may be appropriately reduced and measured at the concentration in which it is completely dissolved. The acidic functional groups at a pH below 8.0 are preferably less than 0.01 mg KOH / g, and more preferably less than 0.001 mg KOH / g. The acidic functional groups at a pH of 8.0 or higher are preferably 3.70 to 22.5 mg KOH / g, and more preferably 4.00 to 18.0 mg KOH / g.

[0123] [Amine Value] From the viewpoint of storage stability of the composition, the amine value of the specific resin is preferably 0.100 mmol / g or less, more preferably 0.0001 to 0.090 mmol / g, and even more preferably 0.001 to 0.080 mmol / g. The lower limit of the above amine value is not particularly limited and may be 0.00 mmol / g. The above amine value was measured by dissolving 0.62 g of resin in 50 mL of diglym, and then adding 10 mL of acetic acid to prepare a measurement solution. This solution was then titrated with an acetic acid solution of 0.01 N (0.01 mol / L) perchloric acid and the neutralization point was detected.

[0124] [Transmittance] When the specific resin is used to form a film with a thickness of 5 μm, the transmittance at a wavelength of 365 nm is preferably 10% or more, more preferably 20% or more, even more preferably 30% or more, and most preferably 50% or more. The upper limit of the above transmittance is not particularly limited and may be 100% or less. The above film can be obtained, for example, by dissolving the specific resin in γ-butyrolactone, coating it on a transparent substrate, and then heating it at 100°C for 5 minutes. Considering solvent solubility, N-methylpyrrolidone or the like may be used instead of γ-butyrolactone. Furthermore, the transparent substrate is not particularly limited as long as it is measurable, and glass substrates, or quartz substrates if greater transparency is required, can be used.

[0125] [Synthesis Method for Specific Resins] As a synthesis method for specific resins, general methods for synthesizing polyamic acid or polyamic acid esters, or polyimides can be used. Specific resins as polyimide precursors can be obtained using methods such as: reacting tetracarboxylic dianhydride with a diamine at low temperature; reacting tetracarboxylic dianhydride with a diamine at low temperature to obtain polyamic acid and then esterifying it with a condensing agent or alkylating agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol and then reacting it with a diamine in the presence of a condensing agent; obtaining a diester from tetracarboxylic dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine. Of the above production methods, the method of obtaining a diester from tetracarboxylic dianhydride with an alcohol and then acid-halogenating the remaining dicarboxylic acid with a halogenating agent and reacting it with a diamine is more preferred. Examples of the condensing agents include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline, 1,1-carbonyldioxy-di-1,2,3-benzotriazole, N,N'-disuccinimidyl carbonate, and trifluoroacetic anhydride. Examples of the alkylating agents include N,N-dimethylformamide dimethylacetal, N,N-dimethylformamide diethylacetal, N,N-dialkylformamide dialkylacetal, trimethyl orthoformate, and triethyl orthoformate. Examples of the halogenating agents include thionyl chloride, oxalyl chloride, and phosphorus oxychloride. In the method for producing the specific resin, it is preferable to use an organic solvent in the reaction. One or more organic solvents may be used. The organic solvent can be appropriately determined depending on the raw materials, but examples include pyridine, diethylene glycol dimethyl ether (diglym), N-methylpyrrolidone, N-ethylpyrrolidone, ethyl propionate, dimethylacetamide, dimethylformamide, tetrahydrofuran, and γ-butyrolactone. In the method for producing specific resins, it is preferable to add a basic compound during the reaction.The basic compound may be one type or two or more types. The basic compound can be appropriately determined depending on the raw materials, but examples include triethylamine, diisopropylethylamine, pyridine, 1,8-diazabicyclo[5.4.0]undeca-7-ene, and N,N-dimethyl-4-aminopyridine.

[0126] As for the synthesis method of polyimide, known methods can be used without particular limitation, such as imidizing the polyimide precursor obtained by the above-described method of synthesizing polyimide precursors by chemical imidation or thermal imidation using an imidation catalyst, or producing it from tetracarboxylic acid and diisocyanate by decarboxylation.

[0127] [Method for purifying tetracarboxylic dianhydride] In order to adjust the ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin, it is preferable to purify commercially available cyclobutanetetracarboxylic dianhydride. Means for increasing the trans conformation of cyclobutane include recrystallization of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, sublimation purification, and photoisomerization.

[0128] Conventional known methods can be used to obtain compounds with a high molar proportion of the trans conformation. While there are no particular limitations, for example, sublimation purification, recrystallization, reprecipitation, zone melting, column purification, and adsorption methods can be used. Sublimation purification is particularly preferred. In sublimation purification, not only sublimable compounds but also compounds that do not sublimate but melt can be used. That is, distillation can be performed using a sublimation purification apparatus. A sublimation purification apparatus, for example, is one that heats and sublimes the compound in a reduced-pressure glass tube, and then separates and recovers the compounds according to their volatility points. For example, a large apparatus capable of sublimation purification of 100 g to 3 kg with a sublimation tube diameter of 300Φ can be used. Maximum temperature 900°C, achievable vacuum 2.7 × 10⁻⁶ －４ Pa can be set. Examples of such equipment include the large sublimation purification system "HX331" (manufactured by NARD Laboratory Co., Ltd.). Alternatively, the sublimation purification system SU-45-800 (manufactured by Asahi Seisakusho Co., Ltd.) can be suitably used.

[0129] Another method for obtaining compounds with a high molar proportion of the trans conformation is to use a photodimerization reaction. For example, maleic anhydride is irradiated with high-pressure mercury lamp light in various solvents, and the precipitated crystals are filtered off. When ethyl acetate or diethyl carbonate is used as the solvent, the molar proportion of the trans conformation can be increased. As a synthesis method that preferentially synthesizes the trans conformation by the above-mentioned photodimerization, the method described in Japanese Patent Application Publication No. 2-61956, the method described in Japanese Patent Application Publication No. 2003-192685, and the method described in Japanese Patent Application Publication No. 2006-328027 can be suitably used.

[0130] -End-Sealing Agents- In the manufacturing method of a specific resin, it is preferable to seal off carboxylic acid anhydrides, acid anhydride derivatives, or amino groups remaining at the ends of the resin, such as polyimide precursors, in order to further improve storage stability. When sealing off carboxylic acid anhydrides and acid anhydride derivatives remaining at the ends of the resin, examples of end-sealing agents include monoalcohols, phenols, thiols, thiophenols, and monoamines. From the perspective of reactivity and film stability, it is more preferable to use monoalcohols, phenols, or monoamines. Preferred monoalcohol compounds include primary alcohols such as methanol, ethanol, propanol, butanol, hexanol, octanol, dodecinol, benzyl alcohol, 2-phenylethanol, 2-methoxyethanol, 2-chloromethanol, and furfuryl alcohol; secondary alcohols such as isopropanol, 2-butanol, cyclohexyl alcohol, cyclopentanol, and 1-methoxy-2-propanol; and tertiary alcohols such as t-butyl alcohol and adamantane alcohol. Preferred phenolic compounds include phenol, methoxyphenol, methylphenol, naphthalene-1-ol, naphthalene-2-ol, hydroxystyrene, and other phenolic compounds.Furthermore, preferred monoamine compounds include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, Examples include 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4,6-dihydroxypyrimidine, 2-aminophenol, 3-aminophenol, 4-aminophenol, 2-aminothiophenol, 3-aminothiophenol, and 4-aminothiophenol. Two or more of these may be used, and multiple different end groups may be introduced by reacting multiple end encapsulants. Furthermore, when encapsulating the amino groups at the ends of the resin, it is possible to encapsulate them with compounds having functional groups that can react with amino groups. Preferred encapsulants for amino groups include carboxylic acid anhydrides, carboxylic acid chlorides, carboxylic acid bromides, sulfonic acid chlorides, sulfonic acid anhydrides, and sulfonic acid carboxylic acid anhydrides, with carboxylic acid anhydrides and carboxylic acid chlorides being more preferred. Preferred carboxylic acid anhydrides include acetic anhydride, propionic anhydride, oxalic acid anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, benzoic anhydride, and 5-norbornene-2,3-dicarboxylic acid anhydride.Furthermore, preferred carboxylic acid chloride compounds include acetyl chloride, acrylate chloride, propionyl chloride, methacrylate chloride, pivaloyl chloride, cyclohexanecarbonyl chloride, 2-ethylhexanoyl chloride, cinnamoyl chloride, 1-adamantane carbonyl chloride, heptafluorobutyryl chloride, stearate chloride, and benzoyl chloride.

[0131] Furthermore, as a terminal encapsulant, it is also preferable to use a compound having a polymerizable group in addition to a functional group that can react with an amino group. The polymerizable group is not limited as long as it can form a new organic bond. Examples of organic bonds that can be formed include carbon-carbon bonds, ester bonds, amide bonds, imide bonds, urea bonds, and urethane bonds. The above organic bonds are formed by radical crosslinking, cationic crosslinking, photodimerization, and by being induced by light or heat from combinations of carboxylic acid-alcohol, carboxylic acid-amine, isocyanate-alcohol, isocyanate-amine, etc. Preferred polymerizable groups include (meth)acrylic groups, styryl groups, carbon-carbon unsaturated groups, maleimide groups, epoxy groups, oxetane groups, and isocyanate groups.

[0132] -Solid Precipitation- The method for producing a specific resin may include a step of precipitating a solid. Specifically, after filtering off the water-absorbing by-products of the dehydrating condensing agent present in the reaction solution as needed, the obtained polymer component is added to a poor solvent such as water, an aliphatic lower alcohol, or a mixture thereof, and the polymer component is precipitated as a solid. By drying this precipitate, a polyimide precursor or the like can be obtained. To improve the degree of purity, the polyimide precursor or the like may be repeatedly redissolved, reprecipitation, and dried. Furthermore, the method may include a step of removing ionic impurities using an ion exchange resin.

[0133] [Examples of specific resins] Specific examples of specific resins include the resins synthesized in the examples.

[0134] [Content] The content of the specific resin in the resin composition of the present invention is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, and even more preferably 30% by mass or more, based on the total solid content of the resin composition. Furthermore, the content of the resin in the resin composition of the present invention is preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. The resin composition of the present invention may contain only one type of specific resin, or it may contain two or more types. When it contains two or more types, it is preferable that the total amount is within the above range.

[0135] <Other Resins> The resin composition of the present invention may also contain other resins different from the specified resin described above (hereinafter also simply referred to as "other resins"). Examples of other resins are resins different from the specified resin, and include polyimide precursors, polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, polyamideimides, phenolic resins, polyamides, epoxy resins, polysiloxanes, resins containing siloxane structures, (meth)acrylic resins, (meth)acrylamide resins, urethane resins, butyral resins, styryl resins, polyether resins, polyester resins, and the like. Examples of other polyimide precursors, other polyimides, polybenzoxazole precursors, polybenzoxazoles, polyamideimide precursors, and polyamideimides include compounds described in paragraphs 0017 to 0138 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0136] When the resin composition of the present invention contains other resins, the content of the other resins is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, even more preferably 1% by mass or more, even more preferably 2% by mass or more, even more preferably 5% by mass or more, and even more preferably 10% by mass or more, based on the total solid content of the resin composition. In the resin composition of the present invention, the content of other resins is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, even more preferably 60% by mass or less, and even more preferably 50% by mass or less, based on the total solid content of the resin composition. In one preferred embodiment of the resin composition of the present invention, the content of other resins is also low. In the above embodiment, the content of other resins is preferably 20% by mass or less, more preferably 15% by mass or less, even more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less, based on the total solid content of the resin composition. The lower limit of the above content is not particularly limited and may be 0% by mass or more. The resin composition of the present invention may contain only one other resin, or it may contain two or more other resins. When it contains two or more other resins, it is preferable that the total amount is within the above range.

[0137] <Polymerizable Compounds> The resin composition of the present invention preferably contains polymerizable compounds different from the above-mentioned resin, and more preferably contains polyfunctional polymerizable compounds different from the above-mentioned resin.

[0138] Examples of polymerizable compounds include polymerizable compounds having radical polymerizable groups (radical crosslinking agents) or other crosslinking agents. Among these, polymerizable compounds having radical polymerizable groups are preferred. The polyfunctional polymerizable compounds described above are preferably polymerizable compounds having two or more radical polymerizable groups.

[0139] [Radical Crosslinking Agent] The resin composition of the present invention preferably contains a radical crosslinking agent. The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the above-mentioned groups containing an ethylenically unsaturated bond include vinyl group, allyl group, vinylphenyl group, (meth)acryloyl group, maleimide group, and (meth)acrylamide group. Among these, (meth)acryloyl group, (meth)acrylamide group, and vinylphenyl group are preferred, and from the viewpoint of reactivity, the (meth)acryloyl group is more preferred.

[0140] The radical crosslinking agent is preferably a compound having one or more ethylenically unsaturated bonds, but more preferably a compound having two or more. The radical crosslinking agent may also have three or more ethylenically unsaturated bonds. Here, the polyfunctional polymerizable compound described above is preferably a compound having two or more ethylenically unsaturated bonds, and may also have three or more ethylenically unsaturated bonds. As for the compound having two or more ethylenically unsaturated bonds, a compound having 2 to 15 ethylenically unsaturated bonds is preferred, a compound having 2 to 10 ethylenically unsaturated bonds is more preferred, and a compound having 2 to 6 is even more preferred. From the viewpoint of the film strength of the resulting pattern (cured product), the resin composition of the present invention may also preferably contain a compound having two ethylenically unsaturated bonds and a compound having three or more ethylenically unsaturated bonds.

[0141] The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and even more preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.

[0142] Specific examples of radical crosslinking agents include unsaturated carboxylic acids (e.g., acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) and their esters and amides, preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds, and amides of unsaturated carboxylic acids and polyhydric amine compounds. Addition reaction products of unsaturated carboxylic acid esters or amides having nucleophilic substituents such as hydroxyl groups, amino groups, or sulfanyl groups with monofunctional or polyfunctional isocyanates or epoxys, and dehydration condensation reaction products with monofunctional or polyfunctional carboxylic acids are also suitably used. Addition reaction products of unsaturated carboxylic acid esters or amides having electrophilic substituents such as isocyanate groups or epoxy groups with monofunctional or polyfunctional alcohols, amines, or thiols, and substitution reaction products of unsaturated carboxylic acid esters or amides having leaving substituents such as halogeno groups or tosyloxy groups with monofunctional or polyfunctional alcohols, amines, or thiols are also suitable. As another example, it is also possible to use a group of compounds in which the above-mentioned unsaturated carboxylic acids are replaced with unsaturated phosphonic acids, vinylbenzene derivatives such as styrene, vinyl ethers, allyl ethers, etc. For specific examples, refer to paragraphs 0113 to 0122 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0143] The radical crosslinking agent is preferably a compound having a boiling point of 100°C or higher under normal pressure. Examples of compounds having a boiling point of 100°C or higher under normal pressure include the compounds described in paragraph 0203 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0144] Other preferred radical crosslinking agents include the radical polymerizable compounds described in paragraphs 0204-0208 of International Publication No. 2021 / 112189. This information is incorporated herein by reference.

[0145] Preferred radical crosslinking agents include dipentaerythritol triacrylate (commercially available as KAYARAD D-330 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol tetraacrylate (commercially available as KAYARAD D-320 (manufactured by Nippon Kayaku Co., Ltd.) and A-TMMT (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), dipentaerythritol penta(meth)acrylate (commercially available as KAYARAD D-310 (manufactured by Nippon Kayaku Co., Ltd.)), dipentaerythritol hexa(meth)acrylate (commercially available as KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd.) and A-DPH (manufactured by Shin Nakamura Chemical Industry Co., Ltd.)), and structures in which the (meth)acryloyl groups of these are linked via ethylene glycol residues or propylene glycol residues. These oligomer types can also be used.

[0146] Commercially available radical crosslinking agents include, for example, SR-494, a tetrafunctional acrylate having four ethylene oxy chains; SR-209, 231, and 239, difunctional methacrylates having four ethylene oxy chains (all manufactured by Sartomer Co., Ltd.); DPCA-60, a hexafunctional acrylate having six pentylene oxy chains; and TPA-330, a trifunctional acrylate having three isobutylene oxy chains (both manufactured by Nippon Kayaku Co., Ltd.); and urethane oligomers. Examples include UAS-10, UAB-140 (both manufactured by Nippon Paper Industries), NK Ester M-40G, NK Ester 4G, NK Ester M-9300, NK Ester A-9300, UA-7200 (all manufactured by Shin Nakamura Chemical Industry Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (all manufactured by Kyoeisha Chemical Co., Ltd.), and Bremmer PME400 (manufactured by NOF Corporation).

[0147] Suitable radical crosslinking agents include urethane acrylates as described in Japanese Patent Publication No. 48-041708, Japanese Unexamined Patent Publication No. 51-037193, Japanese Unexamined Patent Publication No. 02-032293, and Japanese Unexamined Patent Publication No. 02-016765, as well as urethane compounds having an ethylene oxide-based skeleton as described in Japanese Patent Publication No. 58-049860, Japanese Patent Publication No. 56-017654, Japanese Patent Publication No. 62-039417, and Japanese Patent Publication No. 62-039418. Compounds having an amino or sulfide structure within the molecule, as described in Japanese Unexamined Patent Publication No. 63-277653, Japanese Unexamined Patent Publication No. 63-260909, and Japanese Unexamined Patent Publication No. 01-105238, can also be used as radical crosslinking agents.

[0148] The radical crosslinking agent may be a radical crosslinking agent having an acidic group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acidic group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of the aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group. Particularly preferred is a radical crosslinking agent obtained by reacting the unreacted hydroxyl group of an aliphatic polyhydroxy compound with a non-aromatic carboxylic acid anhydride to give it an acidic group, wherein the aliphatic polyhydroxy compound is pentaerythritol or dipentaerythritol. Examples of commercially available products include M-510 and M-520, which are polybasic acid-modified acrylic oligomers manufactured by Toagosei Co., Ltd.

[0149] The acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300 mg KOH / g, and more preferably 1 to 100 mg KOH / g. When the acid value of the radical crosslinking agent is within the above range, it exhibits excellent handling properties during manufacturing and excellent developability. It also exhibits good polymerization properties. The above acid value is measured in accordance with the description in JIS K 0070:1992.

[0150] As a radical crosslinking agent, a radical crosslinking agent having at least one selected from the group consisting of urea bonds and urethane bonds (hereinafter also referred to as "crosslinking agent U") is also preferred. Examples of crosslinking agent U include compounds described in paragraphs 0133 to 0143 of International Publication No. 2023 / 190064. This content is incorporated herein by reference.

[0151] From the viewpoint of pattern resolution and film stretchability, it is preferable to use a bifunctional methacrylate or acrylate in the resin composition. Specific compounds include triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG (polyethylene glycol) 200 diacrylate, PEG 200 dimethacrylate, PEG 600 diacrylate, PEG 600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1,5-pentanediol diacrylate, and 1,6-methyl-1,5-pentanediol diacrylate. Xanediol diacrylate, 1,6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, ethylene oxide (EO) adduct diacrylate of bisphenol A, ethylene oxide (EO) adduct dimethacrylate of bisphenol A, propylene oxide (PO) adduct diacrylate of bisphenol A, PO adduct dimethacrylate of bisphenol A, 2-hydroxy-3-acryloyloxypropyl methacrylate, isocyanuric acid EO-modified diacrylate, isocyanuric acid EO-modified dimethacrylate, and other bifunctional acrylates and bifunctional methacrylates having urethane bonds can be used. Two or more of these can be mixed and used as needed. For example, PEG200 diacrylate refers to polyethylene glycol diacrylate in which the formula weight of the polyethylene glycol chain is about 200. From the viewpoint of suppressing warping of the pattern (cured product), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent in the resin composition of the present invention.Preferably used as monofunctional radical crosslinking agents include (meth)acrylic acid derivatives such as n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, carbitol (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, N-methylol (meth)acrylamide, glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate; N-vinyl compounds such as N-vinylpyrrolidone and N-vinylcaprolactam; and allyl glycidyl ether. To suppress volatilization before exposure, compounds with a boiling point of 100°C or higher under normal pressure are also preferred as monofunctional radical crosslinking agents. Other examples of bifunctional or more functional radical crosslinking agents include allyl compounds such as diallyl phthalate and triallyl trimellitate.

[0152] If a radical crosslinking agent is included, the content of the radical crosslinking agent is preferably more than 0% by mass and 60% by mass or less, relative to the total solid content of the resin composition. The lower limit is more preferably 5% by mass or more. The upper limit is more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0153] A single radical crosslinking agent may be used alone, or two or more may be used in combination. When two or more agents are used in combination, it is preferable that their total amount be within the above range.

[0154] [Other Crosslinking Agents] The resin composition of the present invention may also preferably contain other crosslinking agents different from the radical crosslinking agents described above. Other crosslinking agents refer to crosslinking agents other than the radical crosslinking agents described above, and are preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products upon exposure to a photoacid generator or photobase generator, and more preferably compounds having multiple groups in the molecule that promote the formation of covalent bonds with other compounds in the composition or their reaction products by the action of an acid or base. The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator in the exposure step. Examples of other crosslinking agents include the compounds described in paragraphs 0179 to 0207 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0155] [Photopolymerization Initiator] The resin composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is preferably a photoradical generator (also referred to as a "photoradical polymerization initiator"). There are no particular restrictions on the photoradical polymerization initiator, and it can be appropriately selected from known photoradical polymerization initiators. For example, a photoradical polymerization initiator that is photosensitive to light in the ultraviolet to visible region is preferred. Alternatively, it may be an activator that acts with a photoexcited sensitizer to generate active radicals.

[0156] The photoradical polymerization initiator is present in an amount of at least about 50 L / mol with a wavelength in the range of about 240 to 800 nm (preferably 330 to 500 nm). －１ ・cm －１ It is preferable that the compound contains at least one compound having a molar extinction coefficient. The molar extinction coefficient of the compound can be measured using a known method. For example, it is preferable to measure it using an ultraviolet-visible spectrophotometer (Varian Cary-5 spectrophotometer) with ethyl acetate solvent at a concentration of 0.01 g / L.

[0157] Any known compound can be used as a photoradical polymerization initiator. Examples include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, etc.), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, ketoxime ethers, α-aminoketone compounds such as aminoacetophenone, α-hydroxyketone compounds such as hydroxyacetophenone, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For further details, please refer to paragraphs 0165 to 0182 of Japanese Patent Application Publication No. 2016-027357 and paragraphs 0138 to 0151 of International Publication No. 2015 / 199219, which are incorporated herein by reference. Furthermore, examples include paragraphs 0065 to 0111 of Japanese Patent Publication No. 2014-130173, the compounds described in Japanese Patent No. 6301489, the peroxide-based photopolymerization initiators described in MATERIAL STAGE 37-60p, vol. 19, No. 3, 2019, the photopolymerization initiators described in International Publication No. 2018 / 221177, the photopolymerization initiators described in International Publication No. 2018 / 110179, the photopolymerization initiators described in Japanese Patent Publication No. 2019-043864, the photopolymerization initiators described in Japanese Patent Publication No. 2019-044030, and the peroxide-based initiators described in Japanese Patent Publication No. 2019-167313, the contents of which are incorporated herein by reference.

[0158] Examples of ketone compounds include the compounds described in paragraph 0087 of Japanese Patent Publication No. 2015-087611, the contents of which are incorporated herein by reference. Among commercially available products, Kayacure-DETX-S (manufactured by Nippon Kayaku Co., Ltd.) is also suitably used.

[0159] In one embodiment of the present invention, hydroxyacetophenone compounds, aminoacetophenone compounds, and acylphosphine compounds can be suitably used as photoradical polymerization initiators. More specifically, for example, an aminoacetophenone-based initiator described in Japanese Patent Application Publication No. 10-291969 and an acylphosphine oxide-based initiator described in Japanese Patent No. 4225898 can be used, and this is incorporated herein by reference.

[0160] As α-hydroxyketone initiators, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127 (all manufactured by IGM Resins B.V.), IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE-2959, and IRGACURE 127 (all manufactured by BASF) can be used.

[0161] As α-aminoketone initiators, Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), IRGACURE 907, IRGACURE 369, and IRGACURE 379 (all manufactured by BASF) can be used.

[0162] As aminoacetophenone initiators, acylphosphine oxide initiators, and metallocene compounds, for example, compounds described in paragraphs 0161 to 0163 of International Publication No. 2021 / 112189 can also be suitably used. This is incorporated herein by reference.

[0163] More preferably, oxime compounds are used as photoradical polymerization initiators. Using oxime compounds makes it possible to more effectively improve the exposure latitude. Oxime compounds are particularly preferred because they have a wide exposure latitude (exposure margin) and also act as photocuring accelerators.

[0164] Specific examples of oxime compounds include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-080068, Japanese Patent Publication No. 2006-342166, the compounds described in J. C. S. Perkin II (1979, pp. 1653-1660), the compounds described in J. C. S. Perkin II (1979, pp. 156-162), and Journal of Photopolymer Science and Examples include compounds described in Technology (1995, pp. 202-232), compounds described in Japanese Patent Publication No. 2000-066385, compounds described in Japanese Patent Publication No. 2004-534797, compounds described in Japanese Patent Publication No. 2017-019766, oxime ester compounds having an anthracene skeleton described in Japanese Patent Publication No. 2024-149305, compounds described in Japanese Patent No. 6065596, compounds described in International Publication No. 2015 / 152153, compounds described in International Publication No. 2017 / 051680, compounds described in Japanese Patent Publication No. 2017-198865, compounds described in paragraphs 0025-0038 of International Publication No. 2017 / 164127, and compounds described in International Publication No. 2013 / 167515, the contents of which are incorporated herein by reference.

[0165] Preferred oxime compounds include, for example, compounds with the following structures, as well as 3-(benzoyloxy(imino))butan-2-one, 3-(acetoxy(imino))butan-2-one, 3-(propionyloxy(imino))butan-2-one, 2-(acetoxy(imino))pentan-3-one, 2-(acetoxy(imino))-1-phenylpropane-1-one, 2-(benzoyloxy(imino))-1-phenylpropane-1-one, 3-((4-toluenesulfonyloxy)imino)butan-2-one, and 2-(ethoxycarbonyloxy(imino))-1-phenylpropane-1-one. In resin compositions, it is particularly preferable to use oxime compounds as photoradical polymerization initiators. Oxime compounds used as photoradical polymerization initiators have a >C=N-O-C(=O)- linking group in their molecule.

[0166]

[0167] Commercially available oxime compounds include IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04, IRGACURE OXE 05 (all manufactured by BASF), ADEKA optomer N-1919 (manufactured by ADEKA Corporation, photoradical polymerization initiator 2 described in Japanese Patent Publication No. 2012-014052), TR-PBG-304, TR-PBG-305 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA Arclus NCI-730, NCI-831, and ADEKA Arclus NCI-930 (manufactured by ADEKA Corporation), DFI-091 (manufactured by Daito Chemix Co., Ltd.), and SpeedCure. PDO (manufactured by SARTOMER ARKEMA) is one example. Additionally, oxime compounds with the following structures can be used.

[0168] As photoradical polymerization initiators, for example, oxime compounds having a fluorene ring as described in paragraphs 0169-0171 of International Publication No. 2021 / 112189, oxime compounds having a skeleton in which at least one benzene ring of the carbazole ring is a naphthalene ring, and oxime compounds having a fluorine atom may be used. Also, oxime compounds having a nitro group as described in paragraphs 0208-0210 of International Publication No. 2021 / 020359, oxime compounds having a benzofuran skeleton, and oxime compounds in which a substituent having a hydroxyl group is attached to the carbazole skeleton may be used. These contents are incorporated herein by reference.

[0169] As a photopolymerization initiator, an aromatic ring group Ar, in which an electron-withdrawing group is introduced to the aromatic ring, is used. ＯＸ１ An oxime compound having the above aromatic ring group Ar (hereinafter also referred to as oxime compound OX) can also be used. ＯＸ１Examples of electron-withdrawing groups include acyl groups, nitro groups, trifluoromethyl groups, alkylsulfinyl groups, arylsulfinyl groups, alkylsulfonyl groups, arylsulfonyl groups, and cyano groups. Acyl and nitro groups are preferred, acyl groups are more preferred because they easily form films with excellent light resistance, and benzoyl groups are even more preferred. The benzoyl group may have substituents. Preferred substituents are halogen atoms, cyano groups, nitro groups, hydroxyl groups, alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic groups, heterocyclic oxy groups, alkenyl groups, alkylsulfanyl groups, arylsulfanyl groups, acyl groups, or amino groups. More preferred substituents are alkyl groups, alkoxy groups, aryl groups, aryloxy groups, heterocyclic oxy groups, alkylsulfanyl groups, arylsulfanyl groups, or amino groups. Even more preferred substituents are alkoxy groups, alkylsulfanyl groups, or amino groups.

[0170] The oxime compound OX is preferably at least one selected from the compounds represented by formula (OX1) and the compounds represented by formula (OX2), and more preferably the compound represented by formula (OX2). In the formula, R Ｘ１ R represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, acyloxy group, amino group, phosphinoyl group, carbamoyl group, or sulfamoyl group. Ｘ２ R represents an alkyl group, alkenyl group, alkoxy group, aryl group, aryloxy group, heterocyclic group, heterocyclic oxy group, alkylsulfanyl group, arylsulfanyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyloxy group, or amino group. Ｘ３ ~R Ｘ１４ Each of these independently represents a hydrogen atom or a substituent. However, R Ｘ１０ ~R Ｘ１４At least one of them is an electron-withdrawing group.

[0171] In the above formula, R Ｘ１２ R is an electron-withdrawing group, Ｘ１０ , R Ｘ１１ , R Ｘ１３ , R Ｘ１４ It is preferable that it is a hydrogen atom.

[0172] Specific examples of oxime compounds OX include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600, which are incorporated herein by reference.

[0173] Particularly preferred oxime compounds include oxime compounds having specific substituents as shown in Japanese Patent Publication No. 2007-269779 and oxime compounds having a thioaryl group as shown in Japanese Patent Publication No. 2009-191061, the details of which are incorporated herein by reference.

[0174] From the viewpoint of exposure sensitivity, the photoradical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethylketal compounds, α-hydroxyketone compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and their derivatives, cyclopentadiene-benzene-iron complexes and their salts, halomethyloxadiazole compounds, and 3-arylsubstituted coumarin compounds.

[0175] Furthermore, the photoradical polymerization initiator is a trihalomethyltriazine compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a triarylimidazole dimer, an onium salt compound, a benzophenone compound, or an acetophenone compound. More preferably, at least one compound selected from the group consisting of trihalomethyltriazine compounds, α-aminoketone compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, and benzophenone compounds is preferred, and a metallocene compound or an oxime compound is even more preferred.

[0176] As photoradical polymerization initiators, compounds described in paragraphs 0175-0179 of International Publication No. 2021 / 020359 and compounds described in paragraphs 0048-0055 of International Publication No. 2015 / 125469 may also be used, and this is incorporated herein by reference.

[0177] As the photoradical polymerization initiator, a bifunctional or trifunctional or more photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thus providing good sensitivity. Furthermore, when an asymmetric compound is used, the crystallinity decreases and solubility in solvents etc. improves, making precipitation less likely over time and improving the long-term stability of the resin composition. Specific examples of bifunctional or trifunctional or more photoradical polymerization initiators include dimers of oxime compounds described in JP 2010-527339, JP 2011-524436, International Publication No. 2015 / 004565, paragraphs 0407-0412 of JP 2016-532675, and paragraphs 0039-0055 of International Publication No. 2017 / 033680, as well as compounds (E) and (G) described in JP 2013-522445, and International Publication No. 2016 / 0 Examples include Cmpd1 to 7 described in Patent No. 34963, oxime ester photoinitiators described in paragraph 0007 of Japanese Patent Publication No. 2017-523465, photoinitiators described in paragraphs 0020 to 0033 of Japanese Patent Application Publication No. 2017-167399, photopolymerization initiators (A) described in paragraphs 0017 to 0026 of Japanese Patent Application Publication No. 2017-151342, and oxime ester photoinitiators described in Japanese Patent No. 6469669, the contents of which are incorporated herein by reference.

[0178] Among these, it is preferable that the polymerization initiator is a photoradical generator, and that the photoradical generator is a (keto)oxime ester compound. Examples of (keto)oxime ester compounds include those described in paragraph 0121 of Japanese Patent Application Publication No. 2023-111491, etc. In addition, those used in the embodiments of this application can also be suitably used.

[0179] If the resin composition contains a photopolymerization initiator, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, even more preferably 0.5 to 15% by mass, and even more preferably 1.0 to 10% by mass, based on the total solid content of the resin composition. The resin composition may contain only one type of photopolymerization initiator or two or more types. If two or more types of photopolymerization initiators are contained, it is preferable that the total amount is within the above range. In addition, since photopolymerization initiators may also function as thermal polymerization initiators, crosslinking by the photopolymerization initiator may be further advanced by heating with an oven or hot plate, etc.

[0180] [Amine Compounds] From the viewpoint of resolution, the resin composition preferably contains amine compounds. The amine compound is preferably a compound that acts as a sensitizer, and more preferably a compound that has a sensitizing effect on photoradical polymerization initiators. The sensitizer absorbs specific active radiation and enters an electronically excited state. The sensitizer in the electronically excited state comes into contact with thermal radical polymerization initiators, photoradical polymerization initiators, etc., causing effects such as electron transfer, energy transfer, and heat generation. As a result, the thermal radical polymerization initiators and photoradical polymerization initiators undergo chemical changes and decompose, generating radicals, acids, or bases. In addition, if some of the amine compound remains in the cured product, acids generated in the cured product and acids introduced from outside the cured product are quenched, and as a result the oxidation of metals is suppressed, the adhesion may be improved.

[0181] Preferred amine compounds include compounds containing a benzene ring structure with a dialkylamino group or a dihydroxyalkylamino group as a substituent.

[0182] Examples of amine compounds include Michlaz ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p-dimethylaminocinnamyrideneindanone, p-dimethylaminobenzylideneindanone, 2- (p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbon Nyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin (7-(diethylamino)coumarin-3-carboxylate ethyl), N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinobenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, dimethylaniline, bis(4-dimeth Examples include (p-(p-dimethylaminophenyl)methane, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazol, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzothiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, 2-(p-dimethylaminobenzoyl)styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4'-dimethylacetanilide, etc.

[0183] Among these, the amine compound is preferably the compound represented by the following formula (AN-1) or the following formula (AN-2) (hereinafter also referred to as "compound A"). In formula (AN-1), R １１ and R １２ Each of these independently represents a hydrogen atom or a monovalent organic group, R １１ and R １２ At least one of them contains a group represented by formula (R-1), and Ar １ R represents an aromatic ring structure which may have substituents or fused rings, n1 represents an integer of 2 or more, when n1 is 2, X represents a single bond or a divalent linking group, when n1 is 3 or more, X represents an n1valent linking group. In formula (AN-2), R ２１ and R ２２ Each of these independently represents a hydrogen atom or a monovalent organic group, R ２１ and R ２２ At least one of them contains a group represented by formula (R-1), and Ar ２ represents an aromatic ring structure which may have substituents or fused rings, and n2 represents an integer of 1 or more. In formula (R-1), R Ｒ１ and R Ｒ２ Each of these independently represents a hydrogen atom or a monovalent organic group, and there are m R Ｒ１ Each of them may be the same or different, and there are m R Ｒ２ These elements may be the same or different, m represents an integer greater than or equal to 2, and * represents a connection point with another structure.

[0184] In formula (AN-1), R １１ and R １２ Preferably, all of these are groups represented by formula (R-1). １１ and R １２ If one of them is a hydrogen atom or a monovalent organic group different from the group represented by formula (R-1), then R １１ and R １２ Preferably, one of the groups is a monovalent organic group different from the group represented by formula (R-1). Examples of monovalent organic groups different from the group represented by formula (R-1) include alkyl groups and aryl groups, with alkyl groups being preferred and methyl groups being more preferred.

[0185] In the group represented by formula (R-1), R Ｒ１ and R Ｒ２ Each of these independently represents a hydrogen atom or a monovalent organic group, preferably a hydrogen atom or an alkyl group, and more preferably a hydrogen atom or a methyl group. Ｒ１ and R Ｒ２ It is also a preferred embodiment that all of them are hydrogen atoms. In formula (R-1), m represents an integer of 2 or more, preferably an integer between 2 and 4, more preferably 2 or 3, and even more preferably 2. Specific examples of the group represented by formula (R-1) are given below, but the present invention is not limited thereto. In the following specific examples, * is synonymous with * in formula (R-1).

[0186] In equation (AN-1), Ar １ represents an aromatic ring structure which may have substituents or fused rings. In formula (AN-1), Ar １ The aromatic ring structure may be either an aromatic hydrocarbon ring structure or an aromatic heterocyclic ring structure, but the aromatic hydrocarbon ring structure is preferred, and the benzene ring structure is more preferred. Examples of substituents include alkyl groups, aryl groups, halogen atoms, etc., with alkyl groups being preferred, and methyl groups being more preferred. Examples of fused rings include cycloalkanes, aromatic rings, etc., with cyclopropane rings being preferred.

[0187] In formula (AN-1), n1 represents an integer between 2 and 4, preferably 2 or 3, and more preferably 2.

[0188] In formula (AN-1), when n1 is 2, X represents a single bond or a divalent linking group. The divalent linking group is preferably an alkylene group, a haloalkylene group, an arylene group, or a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as hydroxyl groups or halogen atoms. The alkylene group is preferably an alkylene group having 1 to 4 carbon atoms, and more preferably a methylene group, an ethylene group, or an isopropylene group. The arylene group may be an aromatic hydrocarbon group or an aromatic heterocyclic group, but is preferably an aromatic hydrocarbon group, and more preferably a phenylene group.

[0189] In formula (AN-1), when n1 is 3 or greater, X represents an n1-valent linking group. The n1-valent linking group is preferably an aliphatic hydrocarbon group, an aromatic group, or a combination thereof. The hydrogen atoms in these groups may be substituted with known substituents such as hydroxyl groups. The aliphatic hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably a saturated aliphatic hydrocarbon group having 1 to 4 carbon atoms. The aromatic group is preferably an aromatic hydrocarbon group, and more preferably an aromatic hydrocarbon group having 6 carbon atoms.

[0190] In formula (AN-2), R ２１ and R ２２ A preferred embodiment is R in formula (AN-1). １１ and R １２ This is similar to the preferred embodiment.

[0191] In equation (AN-2), Ar ２ represents an aromatic ring structure which may have substituents or fused rings. Examples of the above aromatic ring structures include a benzene ring structure, a carbazole ring structure, a fluorene ring structure, etc. Examples of the above substituents include alkyl groups, aryl groups, halogen atoms, etc., with alkyl groups being preferred and methyl groups being more preferred. Examples of the above fused rings include cycloalkanes, aromatic rings, etc., with cyclopropane rings being preferred. Below, Ar ２The present invention is not limited to the following specific examples. In the examples below, * represents the bonding site with the nitrogen atom in formula (AN-2).

[0192] In formula (AN-2), n2 is preferably an integer between 1 and 3, and more preferably 1 or 2.

[0193] Among these, compound A is the compound represented by the above formula (AN-1), and R in the above formula (AN-1) １１ and R １２ These are all groups represented by formula (R-1), and the embodiment in which m in formula (R-1) is 2 is preferred. Preferred embodiments of other symbols in the above embodiment are as described in the explanation of formula (AN-1) above.

[0194] The molecular weight of compound A is preferably 1,000 or less, more preferably 800 or less, and even more preferably 500 or less. The lower limit of the molecular weight is not particularly limited, but for example, it is preferably 150 or more, and more preferably 200 or more.

[0195] When the resin composition contains an amine compound, the content of the amine compound is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, based on the total solid content of the resin composition. The amine compound may be used alone or in combination of two or more types.

[0196] Furthermore, other sensitizing dyes may be used as sensitizers. For details regarding sensitizing dyes, please refer to paragraphs 0161 to 0163 of Japanese Patent Application Publication No. 2016-027357, which are incorporated herein by reference.

[0197] [Chain Transfer Agents] The resin compositions of the present invention may contain chain transfer agents. Chain transfer agents are defined, for example, on pages 683-684 of the Polymer Dictionary, Third Edition (edited by the Society of Polymer Science, Japan, 2005). Examples of chain transfer agents include -S-S- and -SO2 molecules. ２Compounds containing -S-, -N-O-, SH, PH, SiH, and GeH, as well as dithiobenzoates, trithiocarbonates, dithiocarbamates, and xanthanthate compounds having a thiocarbonylthio group used in RAFT (Reversible Addition Fragmentation Chain Transfer) polymerization, are used. These can generate radicals by donating hydrogen to low-activity radicals, or by generating radicals after oxidation and deprotonation. Thiol compounds are particularly preferred.

[0198] Furthermore, the chain transfer agent may be a compound described in paragraphs 0152-0153 of International Publication No. 2015 / 199219, which is incorporated herein by reference.

[0199] If the resin composition contains a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, based on 100 parts by mass of the total solid content of the resin composition. There may be only one type of chain transfer agent, or there may be two or more types. If there are two or more types of chain transfer agents, it is preferable that their total content is within the above range.

[0200] Furthermore, a preferred embodiment of the present invention is that the resin composition of the present invention contains two or more polymerization initiators as polymerization initiators. Specifically, it is preferable that the resin composition of the present invention contains a photopolymerization initiator and a thermal polymerization initiator described later, or contains the above-mentioned photoradical polymerization initiator and photoacid generator.

[0201] By including a photopolymerization initiator and a thermal polymerization initiator described later, pattern formation by exposure becomes possible, and radical polymerization also proceeds more easily during curing by the heating process described later, which may improve performance such as chemical resistance. When including a photopolymerization initiator and a thermal polymerization initiator described later, the content ratio of the thermal polymerization initiator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the thermal polymerization initiator.

[0202] The inclusion of a photoradical polymerization initiator and a photoacid generator may improve performance such as resolution. When a photopolymerization initiator and a photoacid generator are included, the content ratio of the photoacid generator is preferably 20 to 70% by mass, and more preferably 30 to 60% by mass, relative to the total content of the photopolymerization initiator and the photoacid generator.

[0203] [Thermal Polymerization Initiators] Examples of thermal polymerization initiators include thermal radical polymerization initiators. Thermal radical polymerization initiators are compounds that generate radicals using thermal energy, thereby initiating or promoting the polymerization reaction of polymerizable compounds. By adding thermal radical polymerization initiators, the polymerization reaction of resins and polymerizable compounds can be advanced, thereby further improving solvent resistance.

[0204] Examples of thermal radical polymerization initiators include the compounds described in paragraphs 0074 to 0118 of Japanese Patent Application Publication No. 2008-063554, the details of which are incorporated herein by reference.

[0205] If a thermal polymerization initiator is included, its content is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 0.5 to 15% by mass, based on the total solid content of the resin composition. Only one thermal polymerization initiator may be included, or two or more may be included. If two or more thermal polymerization initiators are included, the total amount is preferably within the above range.

[0206] <Base Generator> The resin composition of the present invention may contain a base generator. Here, a base generator is a compound that can generate a base by physical or chemical action. Preferred base generators include thermal base generators and photobase generators. In particular, when the resin composition contains a precursor of a cyclized resin, it is preferable that the resin composition contains a base generator. By containing a thermal base generator in the resin composition, the cyclization reaction of the precursor can be promoted by heating, for example, resulting in good mechanical properties and chemical resistance of the cured product, and good performance as an interlayer insulating film for redistribution layers contained in semiconductor packages, for example. The base generator may be an ionic base generator or a nonionic base generator. Examples of bases generated from the base generator include secondary amines and tertiary amines. The base generator is not particularly limited, and known base generators can be used. Known base-generating agents include, for example, carbamoyloxime compounds, carbamoylhydroxylamine compounds, carbamic acid compounds, formamide compounds, acetamide compounds, carbamate compounds, benzylcarbamate compounds, nitrobenzylcarbamate compounds, sulfonamide compounds, imidazole derivative compounds, amineimide compounds, pyridine derivative compounds, α-aminoacetophenone derivative compounds, quaternary ammonium salt derivative compounds, iminium salts, pyridinium salts, α-lactone ring derivative compounds, phthalimide derivative compounds, and acyloxyimino compounds. Specific examples of nonionic base-generating agents include compounds represented by formula (B1), formula (B2), or formula (B3).

[0207] In formulas (B1) and (B2), Rb １ , Rb ２ and Rb ３ Each of these independently represents an organic group that does not have a tertiary amine structure, a halogen atom, or a hydrogen atom. However, Rb １ and Rb ２ They cannot simultaneously become hydrogen atoms. Also, Rb １ , Rb ２ and Rb ３None of these structures have a carboxyl group. In this specification, a tertiary amine structure refers to a structure in which all three bonds of a trivalent nitrogen atom are covalently bonded to carbon atoms of a hydrocarbon group. Therefore, if the carbon atom bonded to the trivalent nitrogen atom is a carbon atom that constitutes a carbonyl group, that is, if it forms an amide group together with the nitrogen atom, it is not a tertiary amine structure.

[0208] In formulas (B1) and (B2), Rb １ , Rb ２ and Rb ３ Preferably, at least one of these components contains a cyclic structure, and more preferably, at least two contain cyclic structures. The cyclic structure may be a monoring or a fused ring, with a monoring or a fused ring formed by the fusion of two monorings being preferred. The monoring is preferably a five-membered ring or a six-membered ring, with a six-membered ring being more preferred. The monoring is preferably a cyclohexane ring or a benzene ring, with a cyclohexane ring being more preferred.

[0209] More specifically, Rb １ and Rb ２ The group is preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12 carbon atoms). These groups may have substituents. Rb １ and Rb ２ These may be bonded to each other to form a ring. The ring formed is preferably a 4- to 7-membered nitrogen-containing heterocycle. Rb １ and Rb ２The group is preferably a substituted linear, branched, or cyclic alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), more preferably a substituted cycloalkyl group (preferably having 3 to 24 carbon atoms, more preferably 3 to 18, and even more preferably 3 to 12 carbon atoms), and even more preferably a substituted cyclohexyl group.

[0210] Rb ３ Examples include alkyl groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryl groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10), alkenyl groups (preferably with 2 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6), arylalkyl groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12), arylalkenyl groups (preferably with 8 to 24 carbon atoms, more preferably 8 to 20, and even more preferably 8 to 16), alkoxy groups (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12), aryloxy groups (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12), or arylalkyloxy groups (preferably with 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 12). Among these, cycloalkyl groups (preferably with 3 to 24 carbon atoms, more preferably with 3 to 18 carbon atoms, and even more preferably with 3 to 12 carbon atoms), arylalkenyl groups, and arylalkyloxy groups are preferred. Rb ３ It may have further substituents.

[0211] The compound represented by formula (B1) is preferably a compound represented by the following formula (B1-1) or formula (B1-2).

[0212] In the formula, Rb １１ and Rb １２ , and Rb ３１ and Rb ３２ These are Rb in equation (B1), respectively. １ and Rb ２ It is the same as Rb １３The group is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 12 carbon atoms), and may have substituents. Among these, Rb １３ An aryl alkyl group is preferred.

[0213] Rb ３３ and Rb ３４ Each of these is independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8, and even more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8, and even more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), and an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11 carbon atoms), with the hydrogen atom being preferred.

[0214] Rb ３５ The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and even more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and even more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and even more preferably with 6 to 12 carbon atoms), and an aryl alkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and even more preferably with 7 to 12 carbon atoms), with the aryl group being preferred.

[0215] The compound represented by formula (B1-1) is preferably the compound represented by formula (B1-1a).

[0216] Rb １１ and Rb １２ Rb in equation (B1-1) １１ and Rb １２ This is synonymous with Rb. １５ and Rb １６Rb is a hydrogen atom, an alkyl group (preferably with 1 to 12 carbon atoms, more preferably with 1 to 6 carbon atoms, and even more preferably with 1 to 3 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 6 carbon atoms, and even more preferably with 2 to 3 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18 carbon atoms, and even more preferably with 6 to 10 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19 carbon atoms, and even more preferably with 7 to 11 carbon atoms), with hydrogen atoms or methyl groups being preferred. １７ The group is an alkyl group (preferably with 1 to 24 carbon atoms, more preferably with 1 to 12, and even more preferably with 3 to 8 carbon atoms), an alkenyl group (preferably with 2 to 12 carbon atoms, more preferably with 2 to 10, and even more preferably with 3 to 8 carbon atoms), an aryl group (preferably with 6 to 22 carbon atoms, more preferably with 6 to 18, and even more preferably with 6 to 12 carbon atoms), and an arylalkyl group (preferably with 7 to 23 carbon atoms, more preferably with 7 to 19, and even more preferably with 7 to 12 carbon atoms), with the aryl group being the most preferred.

[0217]

[0218] In formula (B3), L represents a divalent hydrocarbon group having a saturated hydrocarbon group on the linking chain pathway connecting adjacent oxygen atoms and carbon atoms, and having three or more atoms on the linking chain pathway. Ｎ１ and R Ｎ２ Each of these independently represents a monovalent organic group.

[0219] In this specification, "linking chain" refers to the atomic chain on the path connecting two atoms or groups of atoms to be linked, specifically the one that connects these linked atoms in the shortest possible time (minimum number of atoms). For example, in the compound represented by the following formula, L is composed of a phenyleneethylene group and has an ethylene group as a saturated hydrocarbon group, the linking chain is composed of four carbon atoms, and the number of atoms on the path of the linking chain (i.e., the number of atoms constituting the linking chain, hereinafter also referred to as "linking chain length" or "length of the linking chain") is 4.

[0220] The number of carbon atoms in L in formula (B3) (including carbon atoms other than those in the linking chain) is preferably 3 to 24. The upper limit is more preferably 12 or less, even more preferably 10 or less, and particularly preferably 8 or less. The lower limit is more preferably 4 or more. From the viewpoint of rapidly carrying out the above intramolecular cyclization reaction, the upper limit of the linking chain length of L is preferably 12 or less, more preferably 8 or less, even more preferably 6 or less, and particularly preferably 5 or less. In particular, the linking chain length of L is preferably 4 or 5, and most preferably 4. Specific preferred compounds for the base generator include, for example, the compounds described in paragraphs 0102 to 0168 of International Publication No. 2020 / 066416 and the compounds described in paragraphs 0143 to 0177 of International Publication No. 2018 / 038002.

[0221] Furthermore, the base generator may also preferably contain a compound represented by the following formula (N1).

[0222] In formula (N1), R Ｎ１ and R Ｎ２ Each of these independently represents a monovalent organic group, R Ｃ１ represents a hydrogen atom or protecting group, and L represents a divalent linking group.

[0223] L is a divalent linking group, preferably a divalent organic group. The linking chain length of the linking group is preferably 1 or more, more preferably 2 or more. The upper limit is preferably 12 or less, more preferably 8 or less, and even more preferably 5 or less. The linking chain length is the number of atoms in the shortest path between the two carbonyl groups in the formula.

[0224] In formula (N1), R Ｎ１ and R Ｎ２Each independently represents a monovalent organic group (preferably with 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12 carbon atoms), and is preferably a hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10 carbon atoms). Specifically, examples include an aliphatic hydrocarbon group (preferably with 1 to 24 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 10 carbon atoms) or an aromatic hydrocarbon group (preferably with 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10 carbon atoms), with aliphatic hydrocarbon groups being preferred. Ｎ１ and R Ｎ２ Using an aliphatic hydrocarbon group is preferable because it results in a base with high basicity. The aliphatic hydrocarbon group and aromatic hydrocarbon group may have substituents, and they may also have oxygen atoms in the aliphatic hydrocarbon chain, aromatic ring, or substituent. In particular, an embodiment in which the aliphatic hydrocarbon group has oxygen atoms in the hydrocarbon chain is exemplified.

[0225] R Ｎ１ and R Ｎ２Examples of aliphatic hydrocarbon groups that constitute the group include linear or branched linear alkyl groups, cyclic alkyl groups, groups including combinations of linear and cyclic alkyl groups, and alkyl groups having an oxygen atom in the chain. Linear or branched linear alkyl groups preferably have 1 to 24 carbon atoms, more preferably 2 to 18, and even more preferably 3 to 12. Examples of linear or branched linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, isopropyl, isobutyl, secondary butyl, tertiary butyl, isopentyl, neopentyl, tertiary pentyl, and isohexyl groups. Cyclic alkyl groups preferably have 3 to 12 carbon atoms, and more preferably 3 to 6. Examples of cyclic alkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Groups containing a combination of a linear alkyl group and a cyclic alkyl group preferably have 4 to 24 carbon atoms, more preferably 4 to 18, and even more preferably 4 to 12 carbon atoms. Examples of groups containing a combination of a linear alkyl group and a cyclic alkyl group include cyclohexylmethyl group, cyclohexylethyl group, cyclohexylpropyl group, methylcyclohexylmethyl group, and ethylcyclohexylethyl group. Alkyl groups having an oxygen atom in the chain preferably have 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4 carbon atoms. Alkyl groups having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. In particular, from the viewpoint of increasing the boiling point of the base generating agent described later, R Ｎ１ and R Ｎ２ A C5 to C12 alkyl group is preferred. However, in formulations where adhesion to a metal (e.g., copper) layer is important, a cyclic alkyl group or a C1 to C8 alkyl group is preferred.

[0226] R Ｎ１ and R Ｎ２ These may be linked together to form a cyclic structure. The cyclic structure may have oxygen atoms, etc., in the chain. Also, R Ｎ１ and R Ｎ２The cyclic structure formed may be a monoring or a fused ring, but a monoring is preferred. The cyclic structure formed is preferably a five-membered or six-membered ring containing the nitrogen atom in formula (N1), and examples include a pyrrole ring, imidazole ring, pyrazole ring, pyrroline ring, pyrrolidine ring, imidazolidine ring, pyrazolidine ring, piperidine ring, piperazine ring, and morpholine ring, with pyrroline ring, pyrrolidine ring, piperidine ring, and morpholine ring being preferred.

[0227] R Ｃ１ represents a hydrogen atom or a protecting group, with a hydrogen atom being preferred. Preferred protecting groups are those that decompose upon the action of an acid or base, with acid-decomposed protecting groups being particularly preferred. Specific examples of protecting groups include linear or cyclic alkyl groups or linear or cyclic alkyl groups having an oxygen atom in the chain. Examples of linear or cyclic alkyl groups include methyl, ethyl, isopropyl, tert-butyl, and cyclohexyl groups. Examples of linear alkyl groups having an oxygen atom in the chain include alkyloxyalkyl groups, with methyloxymethyl (MOM) and ethyloxyethyl (EE) groups being preferred. Examples of cyclic alkyl groups having an oxygen atom in the chain include epoxy, glycidyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl (THP) groups.

[0228] In formula (N1), the divalent linking group constituting L is not particularly limited, but a hydrocarbon group is preferred, and an aliphatic hydrocarbon group is more preferred. The hydrocarbon group may have substituents and may have atoms other than carbon atoms in the hydrocarbon chain. The divalent linking group is more preferably a divalent hydrocarbon linking group which may have an oxygen atom in the chain, and even more preferably a group which includes a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain, a divalent aromatic hydrocarbon group, or a combination of a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain and a divalent aromatic hydrocarbon group, and even more preferably a divalent aliphatic hydrocarbon group which may have an oxygen atom in the chain. These groups may not have an oxygen atom. The divalent hydrocarbon linking group preferably has 1 to 24 carbon atoms, more preferably 2 to 12, and even more preferably 2 to 6. The divalent aliphatic hydrocarbon group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The divalent aromatic hydrocarbon group preferably has 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. The group containing a combination of a divalent aliphatic hydrocarbon group and a divalent aromatic hydrocarbon group (e.g., arylene alkyl group) preferably has 7 to 22 carbon atoms, more preferably 7 to 18, and even more preferably 7 to 10.

[0229] The linking group L is preferably a linear or branched linear alkylene group, a cyclic alkylene group, a group including a combination of a linear alkylene group and a cyclic alkylene group, an alkylene group having an oxygen atom in the chain, a linear or branched linear alkenylene group, a cyclic alkenylene group, an arylene group, or an arylenealkylene group. The linear or branched linear alkylene group preferably has 1 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 4. The cyclic alkylene group preferably has 3 to 12 carbon atoms, more preferably 3 to 6. The group including a combination of a linear alkylene group and a cyclic alkylene group preferably has 4 to 24 carbon atoms, more preferably 4 to 12, and even more preferably 4 to 6. The alkylene group having an oxygen atom in the chain may be linear or cyclic, and may be linear or branched. The alkylene group having an oxygen atom in the chain preferably has 1 to 12 carbon atoms, more preferably 1 to 6, and even more preferably 1 to 3 carbon atoms.

[0230] Linear or branched alkenylene groups preferably have 2 to 12 carbon atoms, more preferably 2 to 6, and even more preferably 2 to 3. Linear or branched alkenylene groups preferably have 1 to 10 C=C bonds, more preferably 1 to 6, and even more preferably 1 to 3. Cyclic alkenylene groups preferably have 3 to 12 carbon atoms, more preferably 3 to 6. Cyclic alkenylene groups preferably have 1 to 6 C=C bonds, more preferably 1 to 4, and even more preferably 1 to 2. Arylene groups preferably have 6 to 22 carbon atoms, more preferably 6 to 18, and even more preferably 6 to 10. Arylene alkylene groups preferably have 7 to 23 carbon atoms, more preferably 7 to 19, and even more preferably 7 to 11. Among these, linear alkylene groups, cyclic alkylene groups, alkylene groups having oxygen atoms in the chain, linear alkenylene groups, arylene groups, and arylenealkylene groups are preferred, and 1,2-ethylene groups, propanediyl groups (especially 1,3-propanediyl groups), cyclohexanediyl groups (especially 1,2-cyclohexanediyl groups), vinylene groups (especially cisvinylene groups), phenylene groups (1,2-phenylene groups), phenylenemethylene groups (especially 1,2-phenylenemethylene groups), and ethyleneoxyethylene groups (especially 1,2-ethyleneoxy-1,2-ethylene groups) are more preferred.

[0231] The following commercially available products can be suitably used as photobase generators. For example, WPBG-300, WPBG-345, WPBG-266, WPBG-018, WPBG-027, WPBG-140, WPBG-165 (all WPBG series manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 1,5,7-triazabicyclo[4.4.0]deca-5-ene 2-(9-oxoxanthene-2-yl)propionic acid, 1,5-diazabicyclo[4.3.0]nona-5-ene 2-(9-oxoxanthene-2-yl)propionic acid, and 1,8-diazabicyclo[5.4.0]undeca-7-ene 2-(9-oxoxanthene-2-yl)propionic acid (all manufactured by Tokyo Chemical Industry Co., Ltd.).

[0232] Examples of base-generating agents include, but are not limited to, the following compounds.

[0233]

[0234] The molecular weight of the nonionic base generator is preferably 800 or less, more preferably 600 or less, and even more preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more.

[0235] Specific preferred compounds for ionic base generators include, for example, the compounds described in paragraphs 0148-0163 of International Publication No. 2018 / 038002.

[0236] Specific examples of ammonium salts include, but are not limited to, the following compounds.

[0237] Specific examples of iminium salts include, but are not limited to, the following compounds.

[0238] Furthermore, as a base-generating agent, it is preferable that the amino group is protected by a t-butoxycarbonyl group, from the viewpoint of storage stability and base generation by deprotection during curing.

[0239] Examples of amine compounds protected by a t-butoxycarbonyl group include ethanolamine, 3-amino-1-propanol, 1-amino-2-propanol, 2-amino-1-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 1-amino-2-butanol, 3-amino-2,2-dimethyl-1-propanol, 4-amino-2-methyl-1-butanol, valinol, 3-amino-1,2-propanediol, and 2-amino-1,3-propanediol. Alcohol, tyramine, norephedrine, 2-amino-1-phenyl-1,3-propanediol, 2-aminocyclohexanol, 4-aminocyclohexanol, 4-aminocyclohexaneethanol, 4-(2-aminoethyl)cyclohexanol, N-methylethanolamine, 3-(methylamino)-1-propanol, 3-(isopropylamino)propanol, N-cyclohexylethanolamine, α-[2-(methylamino)ethyl]benzyl alcohol, diethanol Luamine, diisopropanolamine, 3-pyrrolidinol, 2-pyrrolidinemethanol, 4-hydroxypiperidine, 3-hydroxypiperidine, 4-hydroxy-4-phenylpiperidine, 4-(3-hydroxyphenyl)piperidine, 4-piperidinemethanol, 3-piperidinemethanol, 2-piperidinemethanol, 4-piperidineethanol, 2-piperidineethanol, 2-(4-piperidyl)-2-propanol, 1,4-butanol bis(3-aminopropyl) Examples include, but are not limited to, ethers, 1,2-bis(2-aminoethoxy)ethane, 2,2'-oxybis(ethylamine), 1,14-diamino-3,6,9,12-tetraoxatetradecane, 1-aza-15-crown 5-ether, diethylene glycol bis(3-aminopropyl) ether, 1,11-diamino-3,6,9-trioxaundecane, or compounds in which the amino group of an amino acid or its derivative is protected by a t-butoxycarbonyl group.

[0240] When the resin composition contains a base generating agent, the amount of base generating agent is preferably 0.1 to 50 parts by mass per 100 parts by mass of resin in the resin composition. The lower limit is more preferably 0.3 parts by mass or more, and even more preferably 0.5 parts by mass or more. The upper limit is more preferably 30 parts by mass or less, even more preferably 20 parts by mass or less, even more preferably 10 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 4 parts by mass or less. One or more types of base generating agents can be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0241] <Solvent> The resin composition of the present invention preferably contains a solvent. Any known solvent can be used. An organic solvent is preferred. Examples of organic solvents include compounds such as esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, and alcohols.

[0242] Examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ-butyrolactone, ε-caprolactone, δ-valerolactone, γ-valerolactone, alkyloxyacetates (e.g., methyl alkyloxyacetate, ethyl alkyloxyacetate, butyl alkyloxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.)), alkyl esters of 3-alkyloxypropionates (e.g., methyl 3-alkyloxypropionate, ethyl 3-alkyloxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.)), 2-A Suitable examples include alkyl esters of alkyloxypropionates (e.g., methyl 2-alkyloxypropionate, ethyl 2-alkyloxypropionate, propyl 2-alkyloxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkyloxy-2-methylpropionate and ethyl 2-alkyloxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate, ethyl hexanoate, ethyl heptanoate, dimethyl malonate, diethyl malonate, etc.).

[0243] Suitable ethers include, for example, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, diethylene glycol butyl methyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, propylene glycol monopropyl ether acetate, and dipropylene glycol dimethyl ether.

[0244] Suitable ketones include, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, 3-methylcyclohexanone, levoglucocenone, and dihydrolevoglucocenone.

[0245] Suitable cyclic hydrocarbons include, for example, aromatic hydrocarbons such as toluene, xylene, and anisole, and cyclic terpenes such as limonene.

[0246] As an example of a sulfoxide, dimethyl sulfoxide is a suitable choice.

[0247] Suitable amides include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, N,N-dimethylisobutylamide, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, N-formylmorpholine, and N-acetylmorpholine.

[0248] Suitable ureas include N,N,N',N'-tetramethylurea and 1,3-dimethyl-2-imidazolidinone.

[0249] Examples of alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methylphenylcarbinol, n-amyl alcohol, methylamyl alcohol, and diacetone alcohol.

[0250] From the viewpoint of improving the properties of the coated surface, it is also preferable to use a mixture of two or more solvents.

[0251] In the present invention, one solvent selected from methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ-butyrolactone, γ-valerolactone, 3-methoxy-N,N-dimethylpropionamide, toluene, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate, levoglucocenone, and dihydrolevoglucocenone, or a mixed solvent composed of two or more of these, is preferred. The combination of dimethyl sulfoxide and γ-butyrolactone, the combination of dimethyl sulfoxide and γ-valerolactone, the combination of 3-methoxy-N,N-dimethylpropionamide and γ-butyrolactone, the combination of 3-methoxy-N,N-dimethylpropionamide, γ-butyrolactone and dimethyl sulfoxide, or the combination of N-methyl-2-pyrrolidone and ethyl lactate is particularly preferred. Another preferred embodiment of the present invention is to further add toluene to these combined solvents in an amount of about 1 to 10% by mass relative to the total mass of the solvent. In particular, from the viewpoint of storage stability of the resin composition, an embodiment containing γ-valerolactone as the solvent is also a preferred embodiment of the present invention. In such embodiments, the content of γ-valerolactone relative to the total mass of the solvent is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more. Furthermore, the upper limit of the above content is not particularly limited and may be 100% by mass. The above content can be determined by considering the solubility of specific resins and other components contained in the resin composition. Furthermore, when dimethyl sulfoxide and γ-valerolactone are used in combination, it is preferable to contain 60 to 90% by mass of γ-valerolactone and 10 to 40% by mass of dimethyl sulfoxide relative to the total mass of the solvent, more preferably 70 to 90% by mass of γ-valerolactone and 10 to 30% by mass of dimethyl sulfoxide, and even more preferably 75 to 85% by mass of γ-valerolactone and 15 to 25% by mass of dimethyl sulfoxide.

[0252] From the viewpoint of coatability, the solvent content is preferably such that the total solid content concentration of the resin composition of the present invention is 5 to 80% by mass, more preferably 5 to 75% by mass, even more preferably 10 to 70% by mass, and even more preferably 20 to 70% by mass. The solvent content can be adjusted according to the desired thickness of the coating film and the application method. If two or more solvents are included, it is preferable that their total is within the above range.

[0253] <Metal Adhesion Enhancers> The resin composition of the present invention preferably contains a metal adhesion enhancer from the viewpoint of improving adhesion to metal materials used in electrodes, wiring, etc. Examples of metal adhesion enhancers include silane coupling agents having an alkoxysilyl group, aluminum-based adhesion aids, titanium-based adhesion aids, compounds having a sulfonamide structure and compounds having a thiourea structure, phosphoric acid derivative compounds, β-ketoester compounds, amino compounds, and the like.

[0254] [Silane Coupling Agents] Examples of silane coupling agents include the compounds described in paragraph 0316 of International Publication No. 2021 / 112189 and the compounds described in paragraphs 0067 to 0078 of Japanese Patent Publication No. 2018-173573, the contents of which are incorporated herein by reference. It is also preferable to use two or more different silane coupling agents, as described in paragraphs 0050 to 0058 of Japanese Patent Publication No. 2011-128358. The following compounds are also preferable as silane coupling agents. In the following formulas, Me represents a methyl group and Et represents an ethyl group. R below represents a structure derived from a blocking agent in a blocked isocyanate group. The blocking agent can be selected according to the elimination temperature, but examples include alcohol compounds, phenol compounds, pyrazole compounds, triazole compounds, lactam compounds, and active methylene compounds. For example, from the viewpoint of wanting to set the elimination temperature to 160 to 180°C, caprolactam is preferred. Examples of commercially available compounds of this type include X-12-1293 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0255]

[0256] Other silane coupling agents include, for example, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- Examples include (aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltrialkoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-isocyanatetopropyltriethoxysilane, and 3-trimethoxysilylpropyl succinic anhydride. These can be used individually or in combination of two or more. Furthermore, oligomeric compounds having multiple alkoxysilyl groups can also be used as silane coupling agents. Examples of such oligomeric compounds include compounds containing repeating units represented by the following formula (S-1). In formula (S-1), R Ｓ１ represents a monovalent organic group, R Ｓ２ R represents a hydrogen atom, a hydroxyl group, or an alkoxy group, and n represents an integer between 0 and 2. Ｓ１It is preferable that the structure includes polymerizable groups. Examples of polymerizable groups include groups having ethylenically unsaturated bonds, epoxy groups, oxetanyl groups, benzoxazolyl groups, blocked isocyanate groups, amino groups, etc. Examples of groups having ethylenically unsaturated bonds include vinyl groups, allyl groups, isoallyl groups, 2-methylallyl groups, groups having an aromatic ring directly bonded to a vinyl group (e.g., vinylphenyl group), (meth)acrylamide groups, (meth)acryloyloxy groups, etc., with vinylphenyl groups, (meth)acrylamide groups, or (meth)acryloyloxy groups being preferred, vinylphenyl groups or (meth)acryloyloxy groups being more preferred, and (meth)acryloyloxy groups being even more preferred. Ｓ２ n is preferably an alkoxy group, and more preferably a methoxy group or an ethoxy group. n represents an integer from 0 to 2, and is preferably 1. Here, the structures of the repeating units represented by multiple formulas (S-1) contained in the oligomer-type compound may all be the same. Here, it is preferable that n is 1 or 2 in at least one of the repeating units represented by multiple formulas (S-1) contained in the oligomer-type compound, more preferably that n is 1 or 2 in at least two, and even more preferably that n is 1 in at least two. Commercial products can be used as such oligomer-type compounds, and an example of a commercial product is KR-513 (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0257] [Aluminum-based adhesive aids] Examples of aluminum-based adhesive aids include aluminum tris(ethyl acetate), aluminum tris(acetylacetonate), and ethyl acetate aluminum diisopropylate.

[0258] Other metal adhesion modifiers that can be used include the compounds described in paragraphs 0046 to 0049 of Japanese Patent Publication No. 2014-186186 and the sulfide compounds described in paragraphs 0032 to 0043 of Japanese Patent Publication No. 2013-072935, the details of which are incorporated herein by reference.

[0259] The content of the metal adhesion improver is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 10 parts by mass, and even more preferably 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. A value above the lower limit ensures good adhesion between the pattern and the metal layer, while a value below the upper limit ensures good heat resistance and mechanical properties of the pattern. Only one type of metal adhesion improver may be used, or two or more types may be used. If two or more types are used, it is preferable that their total value is within the above range.

[0260] <Migration Inhibitor> The resin composition of the present invention preferably further contains a migration inhibitor. By including a migration inhibitor, for example, when the resin composition is applied to a metal layer (or metal wiring) to form a film, the migration of metal ions originating from the metal layer (or metal wiring) into the film can be effectively suppressed.

[0261] While there are no particular limitations on the migration inhibitors, examples include compounds having heterocyclic rings (pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyrazole ring, isoxazole ring, isothiazole ring, tetrazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, piperidine ring, piperazine ring, morpholine ring, 2H-pyran ring, and 6H-pyran ring, triazine ring), thioureas and compounds having sulfanyl groups, hindered phenol compounds, salicylic acid derivative compounds, and hydrazide derivative compounds. In particular, triazole compounds such as 1,2,4-triazole, benzotriazole, 3-amino-1,2,4-triazole, and 3,5-diamino-1,2,4-triazole, and tetrazole compounds such as 1H-tetrazole, 5-phenyltetrazole, and 5-amino-1H-tetrazole can be preferably used.

[0262] As migration inhibitors, ion trapping agents that capture anions such as halogen ions can also be used.

[0263] Other migration inhibitors that can be used include the rust inhibitor described in paragraph 0094 of Japanese Patent Publication No. 2013-015701, the compounds described in paragraphs 0073 to 0076 of Japanese Patent Publication No. 2009-283711, the compounds described in paragraph 0052 of Japanese Patent Publication No. 2011-059656, the compounds described in paragraphs 0114, 0116 and 0118 of Japanese Patent Publication No. 2012-194520, and the compounds described in paragraph 0166 of International Publication No. 2015 / 199219, the details of which are incorporated herein by reference.

[0264] Specific examples of migration inhibitors include the following compounds.

[0265]

[0266] When the resin composition of the present invention contains a migration inhibitor, the content of the migration inhibitor is preferably 0.01 to 5.0% by mass, more preferably 0.05 to 2.0% by mass, and even more preferably 0.1 to 1.0% by mass, based on the total solid content of the resin composition.

[0267] There may be only one type of migration inhibitor, or there may be two or more types. If there are two or more types of migration inhibitors, it is preferable that their total number is within the above range.

[0268] <Light Absorbers> The resin composition of the present invention may also preferably contain a compound (light absorber) whose absorbance at the exposure wavelength decreases upon exposure. Examples of light absorbers include the compounds described in paragraphs 0159 to 0183 of International Publication No. 2022 / 202647 and the compounds described in paragraphs 0088 to 0108 of Japanese Patent Application Publication No. 2019-206689. These contents are incorporated herein by reference.

[0269] <Polymerization Inhibitor> The resin composition of the present invention preferably contains a polymerization inhibitor. Examples of polymerization inhibitors include phenolic compounds, quinone compounds, amino compounds, N-oxyl free radical compounds, nitro compounds, nitroso compounds, heteroaromatic compounds, and metal compounds.

[0270] Specific examples of polymerization inhibitors include the compounds described in paragraph 0310 of International Publication No. 2021 / 112189, p-hydroquinone, o-hydroquinone, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, phenoxazine, 1,4,4-trimethyl-2,3-diazabicyclo[3.2.2]nona-2-ene-N,N-dioxide, and the like. This information is incorporated herein by reference.

[0271] If the resin composition of the present invention contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20% by mass, more preferably 0.02 to 15% by mass, and even more preferably 0.05 to 10% by mass, based on the total solid content of the resin composition.

[0272] There may be only one polymerization inhibitor or two or more. If there are two or more polymerization inhibitors, it is preferable that their total number is within the above range.

[0273] <Other Additives> The resin composition of the present invention may optionally contain various additives, such as surfactants, higher fatty acid derivatives, thermal polymerization initiators, inorganic particles, ultraviolet absorbers, organotitanium compounds, antioxidants, photoacid generators, anti-aggregation agents, phenolic compounds, other polymer compounds, plasticizers, and other auxiliary agents (e.g., defoamers, flame retardants, etc.), to the extent that the effects of the present invention are obtained. By appropriately including these components, properties such as film properties can be adjusted. These components can be described, for example, in paragraphs 0183 onwards of Japanese Patent Application Publication No. 2012-003225 (paragraph 0237 of the corresponding US Patent Application Publication No. 2013 / 0034812), paragraphs 0101 to 0104, 0107 to 0109 of Japanese Patent Application Publication No. 2008-250074, and these contents are incorporated herein. When these additives are included, their total content is preferably 3% by mass or less of the solid content of the resin composition of the present invention.

[0274] [Surfactants] Various surfactants can be used as surfactants, such as fluorine-based surfactants, silicone-based surfactants, and hydrocarbon-based surfactants. The surfactant may be a nonionic surfactant, a cationic surfactant, or an anionic surfactant.

[0275] By incorporating a surfactant into the resin composition of the present invention, the liquid properties (especially the fluidity) of the prepared coating liquid composition are further improved, and the uniformity of the coating thickness and the liquid-saving properties can be further enhanced. Specifically, when forming a film using a coating liquid containing a surfactant, the interfacial tension between the surface to be coated and the coating liquid decreases, improving the wettability to the surface to be coated and improving the coatability to the surface to be coated. Therefore, it is possible to more favorably form a uniform film with less thickness variation.

[0276] Examples of fluorinated surfactants include the compounds described in paragraph 0328 of International Publication No. 2021 / 112189, which are incorporated herein by reference. Fluorinated polymer compounds can also be preferably used as fluorinated surfactants, which include repeating units derived from a (meth)acrylate compound having a fluorine atom and repeating units derived from a (meth)acrylate compound having two or more (preferably five or more) alkylene oxy groups (preferably ethylene oxy groups, propylene oxy groups). Examples include the following compounds.

[0277] The weight-average molecular weight of the above compound is preferably 3,000 to 50,000, and more preferably 5,000 to 30,000. As a fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in its side chain can also be used. Specific examples include the compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of Japanese Patent Application Publication No. 2010-164965, the contents of which are incorporated herein by reference. Examples of commercially available products include Megafac RS-101, RS-102, RS-718K, etc., manufactured by DIC Corporation.

[0278] The fluorine content in the fluorinated surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. Fluorinated surfactants with a fluorine content within this range are effective in terms of uniformity of coating film thickness and liquid saving, and also have good solubility in the composition.

[0279] Examples of silicone-based surfactants, hydrocarbon-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants include the compounds described in paragraphs 0329-0334 of International Publication No. 2021 / 112189, respectively, which are incorporated herein by reference.

[0280] One type of surfactant may be used, or two or more types may be used in combination. The surfactant content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the composition.

[0281] [Inorganic Particles] Examples of inorganic particles include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, and glass.

[0282] The average particle diameter of the inorganic particles is preferably 0.01 to 2.0 μm, more preferably 0.02 to 1.5 μm, even more preferably 0.03 to 1.0 μm, and particularly preferably 0.04 to 0.5 μm. The above average particle diameter of the inorganic particles is the primary particle diameter and also the volume-average particle diameter. The volume-average particle diameter can be measured, for example, by dynamic light scattering using Nanotrac WAVE II EX-150 (manufactured by Nikkiso Co., Ltd.). If the above measurement is difficult, it can also be measured by centrifugal sedimentation light transmission, X-ray transmission, or laser diffraction / scattering.

[0283] [Organotitanium Compounds] By including organotitanium compounds in the resin composition, a resin layer with excellent chemical resistance can be formed even when cured at low temperatures.

[0284] Suitable organotitanium compounds include those in which an organic group is bonded to a titanium atom via covalent or ionic bonds. Specific examples of organotitanium compounds are shown in I) to VII) below: I) Titanium chelate compounds: Titanium chelate compounds having two or more alkoxy groups are more preferred because they provide good storage stability for the resin composition and yield a good curing pattern. Specific examples include titanium bis(triethanolamine)diisopropoxide, titanium di(n-butoxide)bis(2,4-pentanedione), titanium diisopropoxidebis(2,4-pentanedione), titanium diisopropoxidebis(tetramethylheptanedione), titanium diisopropoxidebis(ethylacetoacetate), etc. II) Tetraalkoxy titanium compounds: For example, titanium tetra(n-butoxide), titanium tetraethoxide, titanium tetra(2-ethylhexoxide), titanium tetraisobutoxide, titanium tetraisopropoxide, titanium tetramethoxide, titanium tetramethoxypropoxide, titanium tetramethylphenoxide, titanium tetra(n-nonyloxide), titanium tetra(n-propoxide), titanium tetrastearaloxide, titanium tetrakis[bis{2,2-(alyloxymethyl)butoxide}], etc. III) Titanocene compounds: For example, pentamethylcyclopentadienyltitanium trimethoxide, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluorophenyl)titanium, bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium, etc. IV) Monoalkoxy titanium compounds: For example, titanium tris(dioctyl phosphate) isopropoxide, titanium tris(dodecylbenzenesulfonate) isopropoxide, etc. V) Titanium oxide compounds: For example, titanium oxide bis(pentanedionate), titanium oxide bis(tetramethylheptanedionate), phthalocyanine titanium oxide, etc.VI) Titanium tetraacetylacetonate compounds: For example, titanium tetraacetylacetonate. VII) Titanate coupling agents: For example, isopropyltridodecylbenzenesulfonyl titanate.

[0285] In particular, from the viewpoint of better chemical resistance, the organotitanium compound is preferably at least one compound selected from the group consisting of I) titanium chelate compounds, II) tetraalkoxytitanium compounds, and III) titanocene compounds. Titanium diisopropoxide bis(ethyl acetoacetate), titanium tetra(n-butoxide), and bis(η5-2,4-cyclopentadien-1-yl)bis(2,6-difluoro-3-(1H-pyrrole-1-yl)phenyl)titanium are preferred.

[0286] Furthermore, it is preferable to include a compound represented by the following formula (T-1) as an organotitanium compound, or in place of an organotitanium compound. In equation (T-1), M is titanium, zirconium, or hafnium, l1 is an integer from 0 to 2, l2 is 0 or 1, l1 + l2 × 2 is an integer from 0 to 2, m is an integer from 0 to 4, n is an integer from 0 to 2, l1 + l2 + m + n × 2 = 4, R １１ Each of these is independently a substituted or unsubstituted cyclopentadienyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted phenoxy group, R １２ R is a substituted or unsubstituted hydrocarbon group, ２ Each of these is an independent group containing a structure represented by the following formula (T-2), and R ３ Each of these is an independent group containing a structure represented by the following formula (T-2), and X Ａ Each of these is independently either an oxygen atom or a sulfur atom. In formula (T-2), X １ ~X ３ Each of these independently represents -C(-*)= or -N=, where * represents a bonding site with another structure, and # represents a bonding site with a metal atom.

[0287] In formula (T-1), from the viewpoint of storage stability of the composition, M is preferably titanium. In formula (T-1), an embodiment in which l1 and l2 are 0 is also one of the preferred embodiments of the present invention. In formula (T-1), m is preferably 2 or 4, and more preferably 2. In formula (T-1), n ​​is preferably 1 or 2, and more preferably 1. Here, in formula (T-1), it is also preferable that l1 and l2 are 0 and m is 0, 2, or 4.

[0288] In formula (T-1), from the viewpoint of the stability of the specific metal complex, R １１ A substituted or unsubstituted cyclopentadienyl ligand is preferred. Also, R １１ The cyclopentadienyl group, alkoxy group, and phenoxy group in the compound may be substituted, but an unsubstituted configuration is also a preferred embodiment of the present invention.

[0289] In formula (T-1), R １２ R is preferably a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrocarbon group having 2 to 10 carbon atoms. １２ The hydrocarbon group in may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group, but an aromatic hydrocarbon group is preferred. The aliphatic hydrocarbon group may be either a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group, but a saturated aliphatic hydrocarbon group is preferred. The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 10 carbon atoms, and even more preferably a phenylene group. １２ The substituents in are preferably monovalent substituents, such as halogen atoms. １２ If is an aromatic hydrocarbon group, it may have an alkyl group as a substituent. Among these, in formula (T-1), R １２ It is preferable that R is an unsubstituted phenylene group. １２ The phenylene group in this is preferably a 1,2-phenylene group.

[0290] In equation (T-1), m is 2 or greater, and R ２ If there are two or more of them, then the two or more R２ The structures of each may be the same or different. In equation (T-1), n ​​is 2 or greater, and R ３ If there are two or more of them, then the two or more R ３ The structures of each may be the same or different.

[0291] In formula (T-2), X １ ~X ３ Each of these independently represents -C(-*)= or -N=, preferably at least one represents -C(-*)=, and more preferably at least two represent -C(-*)=.

[0292] Specific examples of compounds represented by formula (T-1) include, but are not limited to, the compounds used in the examples.

[0293] When an organic titanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better.

[0294] When an organotitanium compound is included, its content is preferably 0.05 to 10 parts by mass, and more preferably 0.1 to 2 parts by mass, per 100 parts by mass of the specific resin. When the content is 0.05 parts by mass or more, the heat resistance and chemical resistance of the resulting cured pattern are better, and when it is 10 parts by mass or less, the storage stability of the composition is better. Other additives include compounds described in paragraphs 0249 to 0282 and 0316 to 0358 of International Publication No. 2022 / 145355. The above description is incorporated herein by reference.

[0295] <Characteristics of the Resin Composition> The viscosity of the resin composition of the present invention can be adjusted by the solid content concentration of the resin composition. From the viewpoint of coating film thickness, 1,000 mm ２ / s~12,000mm ２ / s is preferred, and 2,000 mm ２ / s~10,000mm ２ / s is more preferable, 2,500 mm ２ / s~8,000mm ２ / s is even more preferable. Within the above range, it becomes easier to obtain a highly uniform coating film. 1,000 mm ２ If the temperature is 1 / s or higher, it is easy to coat the film with the required thickness, for example, as an insulating film for rewiring, and 12,000 mm ２ If the rate is less than or equal to / s, a coating with excellent properties can be obtained on the coated surface.

[0296] When a film with a thickness of 10 μm is formed using the resin composition of the present invention, the transmittance of the film at a wavelength of 365 nm is preferably 15% or more, more preferably 20% or more, and even more preferably 25% or more. The upper limit of the transmittance is not particularly limited and may be 100%. The film can be obtained, for example, by coating a silicon wafer with the resin composition of the present invention and then drying it at 100°C for 5 minutes.

[0297] <Restrictions on the substances contained in the resin composition> The water content of the resin composition of the present invention is preferably less than 2.0% by mass, more preferably less than 1.5% by mass, and even more preferably less than 1.0% by mass. If it is less than 2.0%, the storage stability of the resin composition is improved. Methods for maintaining the water content include adjusting the humidity under storage conditions and reducing the porosity of the storage container during storage.

[0298] From the viewpoint of insulating properties, the metal content of the resin composition of the present invention is preferably less than 5 ppm by mass (parts per million), more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of metals include sodium, potassium, magnesium, calcium, iron, copper, chromium, and nickel, but excludes metals included as complexes between organic compounds and metals. If multiple metals are included, it is preferable that the sum of these metals is within the above range.

[0299] Furthermore, methods for reducing metal impurities unintentionally included in the resin composition of the present invention include selecting raw materials with a low metal content as the raw materials constituting the resin composition of the present invention, performing filter filtration on the raw materials constituting the resin composition of the present invention, and performing distillation under conditions in which contamination is suppressed as much as possible by lining the inside of the apparatus with polytetrafluoroethylene or the like.

[0300] When considering the application of the resin composition of the present invention as a semiconductor material, the halogen atom content is preferably less than 500 ppm by mass, more preferably less than 300 ppm by mass, and even more preferably less than 200 ppm by mass, from the viewpoint of wiring corrosion. In particular, the halogen atoms present in the form of halogen ions are preferably less than 5 ppm by mass, more preferably less than 1 ppm by mass, and even more preferably less than 0.5 ppm by mass. Examples of halogen atoms include chlorine atoms and bromine atoms. It is preferable that the total amount of chlorine atoms and bromine atoms, or chlorine ions and bromine ions, is within the above ranges. A preferred method for adjusting the halogen atom content is ion exchange treatment.

[0301] Conventional containers can be used as containers for the resin composition of the present invention. To suppress the incorporation of impurities into the raw materials and the resin composition of the present invention, it is also preferable to use multilayer bottles with an inner wall constructed of six types of resin in six layers, or bottles with a seven-layer structure of six types of resin. Examples of such containers include the container described in Japanese Patent Application Publication No. 2015-123351.

[0302] <Cured product of the resin composition> A cured product of the resin composition of the present invention can be obtained by curing the resin composition of the present invention. The cured product of the present invention is a cured product obtained by curing the resin composition. The curing of the resin composition is preferably done by heating, with a heating temperature of 120°C to 400°C being more preferably, 140°C to 380°C being even more preferably, and 170°C to 350°C being particularly preferred. The form of the cured product of the resin composition is not particularly limited and can be selected according to the application, such as in the form of a film, rod, sphere, or pellet. In the present invention, the cured product is preferably in the form of a film. By pattern processing of the resin composition, the shape of the cured product can also be selected according to the application, such as forming a protective film on the wall surface, forming via holes for conductivity, adjusting impedance, capacitance or internal stress, or providing a heat dissipation function. The film thickness of the cured product (film made of the cured product) is preferably 0.5 μm or more and 150 μm or less. The shrinkage rate when the resin composition of the present invention is cured is preferably 50% or less, more preferably 45% or less, and even more preferably 40% or less. Here, the shrinkage rate refers to the percentage change in volume of the resin composition before and after curing, and can be calculated using the following formula: Shrinkage rate [%] = 100 - (Volume after curing ÷ Volume before curing) × 100

[0303] <Characteristics of the Cured Resin Composition> The imidization reaction rate of the cured resin composition of the present invention is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. If it is 70% or more, the cured product may have excellent mechanical properties. The elongation at break of the cured resin composition of the present invention is preferably 30% or more, more preferably 40% or more, and even more preferably 50% or more. The glass transition temperature (Tg) of the cured resin composition of the present invention is preferably 180°C or higher, more preferably 210°C or higher, and even more preferably 230°C or higher.

[0304] <Preparation of Resin Composition> The resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited and can be carried out by conventionally known methods. Mixing methods include mixing with a stirring blade, mixing with a ball mill, and mixing by rotating a tank. The temperature during mixing is preferably 10 to 30°C, and more preferably 15 to 25°C.

[0305] For the purpose of removing foreign matter such as dirt and fine particles from the resin composition of the present invention, filtration using a filter is preferable. The filter pore size is preferably, for example, 5 μm or less, more preferably 1 μm or less, even more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon. If the filter material is polyethylene, it is more preferably HDPE (high-density polyethylene). The filter may be one that has been pre-washed with an organic solvent. In the filter filtration process, multiple types of filters may be connected in series or in parallel. When multiple types of filters are used, filters with different pore sizes or materials may be combined. As an example of a connection configuration, an HDPE filter with a pore size of 1 μm is connected in series as the first stage, and an HDPE filter with a pore size of 0.2 μm is connected in series as the second stage. Furthermore, various materials may be filtered multiple times. When filtering multiple times, circulating filtration may be used. Furthermore, filtration may be performed under pressure. When filtration is performed under pressure, the pressure applied is preferably, for example, 0.01 MPa to 1.0 MPa, more preferably 0.03 MPa to 0.9 MPa, even more preferably 0.05 MPa to 0.7 MPa, and even more preferably 0.05 MPa to 0.5 MPa. In addition to filtration using a filter, impurity removal treatment using an adsorbent may also be performed. Filter filtration and impurity removal treatment using an adsorbent may be combined. As the adsorbent, known adsorbents can be used. Examples include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon. After filtration using a filter, the resin composition filled into bottles may be subjected to a degassing step by placing it under reduced pressure.

[0306] (Method for Manufacturing Cured Products) The method for manufacturing cured products of the present invention preferably includes a film-forming step of applying a resin composition onto a substrate to form a film. The method for manufacturing cured products more preferably includes the film-forming step, an exposure step of selectively exposing the film formed in the film-forming step, and a developing step of developing the film exposed in the exposure step using a developer to form a pattern. The method for manufacturing cured products particularly preferably includes the film-forming step, the exposure step, the developing step, and at least one of a heating step of heating the pattern obtained in the developing step and a post-development exposure step of exposing the pattern obtained in the developing step. Furthermore, the method for manufacturing cured products may also preferably include the film-forming step and a step of heating the film. Details of each step will be described below.

[0307] <Membrane Formation Process> The resin composition of the present invention can be used in a membrane formation process in which it is applied to a substrate to form a film. The method for producing a cured product of the present invention preferably includes a membrane formation process in which the resin composition is applied to a substrate to form a film.

[0308] [Substrate] The type of substrate can be appropriately determined according to the application and is not particularly limited. Examples of substrates include semiconductor manufacturing substrates such as silicon, silicon nitride, polysilicon, silicon oxide, and amorphous silicon; quartz, glass, optical films, ceramic materials, vapor-deposited films, magnetic films, reflective films; metal substrates such as Ni, Cu, Cr, and Fe (for example, substrates formed from metal, and substrates in which a metal layer is formed by, for example, plating or vapor deposition); paper, SOG (Spin On Glass), TFT (thin film transistor) array substrates, molded substrates, and electrode plates for plasma display panels (PDPs). Semiconductor manufacturing substrates are particularly preferred, and silicon substrates, Cu substrates, and molded substrates are more preferred. These substrates may have layers such as an adhesion layer or an oxide layer made of hexamethyldisilazane (HMDS) on their surface. The shape of the substrate is not particularly limited and may be circular or rectangular. If the substrate is circular, for example, a diameter of 100 to 450 mm is preferred, and 200 to 450 mm is more preferred. If it is rectangular, for example, the length of the shorter side is preferred to be 100 to 1000 mm, and 200 to 700 mm is more preferred. As the substrate, for example, a plate-shaped, preferably panel-shaped, substrate (substrate) is used.

[0309] When a resin composition is applied to the surface of a resin layer (for example, a layer made of cured material) or a metal layer to form a film, the resin layer or metal layer serves as the substrate.

[0310] Coating is a preferred method for applying the resin composition onto a substrate. Specific application methods include dip coating, air knife coating, curtain coating, wire bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and inkjet coating. From the viewpoint of uniformity of film thickness, spin coating, slit coating, spray coating, or inkjet coating are preferred, and from the viewpoint of uniformity of film thickness and productivity, spin coating and slit coating are more preferred. By adjusting the solid content concentration of the resin composition and the coating conditions according to the application method, a film of the desired thickness can be obtained. Furthermore, the coating method can be appropriately selected depending on the shape of the substrate; for circular substrates such as wafers, spin coating, spray coating, and inkjet coating are preferred, while for rectangular substrates, slit coating, spray coating, and inkjet coating are preferred. In the case of spin coating, for example, it can be applied at a rotation speed of 500 to 3,500 rpm for about 10 seconds to 3 minutes. Alternatively, a method can be applied in which a coating film, which has been formed in advance on a temporary support using the above application method, is transferred onto the substrate. Regarding the transfer method, the manufacturing methods described in paragraphs 0023, 0036-0051 of Japanese Patent Application Publication No. 2006-023696 and paragraphs 0096-0108 of Japanese Patent Application Publication No. 2006-047592 can be suitably used. Furthermore, a step to remove excess film from the edges of the substrate may be performed. Examples of such steps include edge bead rinsing (EBR) and back rinsing. A pre-wetting step may also be employed in which various solvents are applied to the substrate before applying the resin composition to improve the wettability of the substrate before applying the resin composition.

[0311] <Drying Process> After the film formation process (layer formation process), the film may be subjected to a drying process to remove the solvent from the formed film (layer). That is, the method for producing a cured product of the present invention may include a drying process for drying the film formed in the film formation process. The drying process is preferably performed after the film formation process and before the exposure process. The drying temperature of the film in the drying process is preferably 50 to 150°C, more preferably 70 to 130°C, and even more preferably 90 to 110°C. Drying may also be performed under reduced pressure. The drying time is exemplified as 30 seconds to 20 minutes, preferably 1 to 10 minutes, and more preferably 2 to 7 minutes.

[0312] <Exposure Process> The above film may be subjected to an exposure process in which the film is selectively exposed. The method for manufacturing the cured product may include an exposure process in which the film formed by the film formation process is selectively exposed. Selective exposure means exposing a part of the film. By selective exposure, exposed areas (exposed parts) and unexposed areas (unexposed parts) are formed in the film. The amount of exposure is not particularly limited as long as the resin composition of the present invention can be cured, but for example, it may be 50 to 10,000 mJ / cm in terms of exposure energy at a wavelength of 365 nm. ２ Preferably, 200 to 8,000 mJ / cm² ２ This is preferable.

[0313] The exposure wavelength can be appropriately determined within the range of 190 to 1,000 nm, with 240 to 550 nm being preferred.

[0314] In relation to the light source, the exposure wavelength can be found in: (1) semiconductor lasers (wavelengths 830nm, 532nm, 488nm, 405nm, 375nm, 355nm, etc.), (2) metal halide lamps, (3) high-pressure mercury lamps, g-line (wavelength 436nm), h-line (wavelength 405nm), i-line (wavelength 365nm), broad (three wavelengths: g, h, i), (4) excimer lasers, KrF excimer laser (wavelength 248nm), ArF excimer laser (wavelength 193nm), F ２Examples of exposures include (5) excimer laser (wavelength 157 nm), (6) extreme ultraviolet light; EUV (wavelength 13.6 nm), (7) YAG laser with second harmonic 532 nm and third harmonic 355 nm. For the resin composition of the present invention, exposure with a high-pressure mercury lamp is particularly preferred, and exposure with the i-line is more preferred from the viewpoint of exposure sensitivity. The exposure method is not particularly limited, and any method in which at least a part of the film made of the resin composition of the present invention is exposed is acceptable, but examples include exposure using a photomask and exposure by laser direct imaging.

[0315] <Post-exposure heating step> The above film may be subjected to a heating step after exposure (post-exposure heating step). That is, the method for producing a cured product of the present invention may include a post-exposure heating step in which the film exposed in the exposure step is heated. The post-exposure heating step can be performed after the exposure step and before the development step. The heating temperature in the post-exposure heating step is preferably 50°C to 140°C, and more preferably 60°C to 120°C. The heating time in the post-exposure heating step is preferably 30 seconds to 300 minutes, and more preferably 1 minute to 10 minutes. The heating rate in the post-exposure heating step is preferably 1 to 12°C / min from the temperature at the start of heating to the maximum heating temperature, more preferably 2 to 10°C / min, and even more preferably 3 to 10°C / min. The heating rate may also be changed as appropriate during heating. The heating means in the post-exposure heating step is not particularly limited, and known hot plates, ovens, infrared heaters, etc., can be used. Furthermore, it is preferable to carry out the heating process in a low-oxygen atmosphere by flowing inert gases such as nitrogen, helium, or argon through the system.

[0316] <Development Process> The film after exposure may be subjected to a development process in which a pattern is formed by developing it with a developer. That is, the method for manufacturing a cured product of the present invention may include a development process in which a pattern is formed by developing the film exposed in the exposure process with a developer. By developing, one of the exposed and unexposed parts of the film is removed, and a pattern is formed. Here, development in which the unexposed part of the film is removed by the development process is called negative development, and development in which the exposed part of the film is removed by the development process is called positive development.

[0317] [Developer] Developers used in the developing process include alkaline aqueous solutions or developers containing organic solvents.

[0318] When the developer is an alkaline aqueous solution, the basic compounds that the alkaline aqueous solution may contain include inorganic alkalis, primary amines, secondary amines, tertiary amines, and quaternary ammonium salts. Preferably, TMAH (tetramethylammonium hydroxide), potassium hydroxide, sodium carbonate, sodium hydroxide, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, tetrapentylammonium hydroxide, tetrahexylammonium hydroxide, tetraoctylammonium hydroxide, ethyltrimethylammonium hydroxide, butyltrimethylammonium hydroxide, methyltriamylammonium hydroxide, dibutyldipentylammonium hydroxide, dimethylbis(2-hydroxyethyl)ammonium hydroxide, trimethylphenylammonium hydroxide, trimethylbenzylammonium hydroxide, triethylbenzylammonium hydroxide, pyrrole, and piperidine are preferred, and TMAH is more preferred. The content of basic compounds in the developer is preferably 0.01 to 10% by mass, more preferably 0.1 to 5% by mass, and even more preferably 0.3 to 3% by mass, based on the total mass of the developer.

[0319] If the developer contains an organic solvent, the organic solvent may be one of the compounds described in paragraph 0387 of International Publication No. 2021 / 112189. This is incorporated herein by reference. Suitable alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutylcarbinol, triethylene glycol, etc., and suitable amides include N-methylpyrrolidone, N-ethylpyrrolidone, dimethylformamide, etc.

[0320] When the developer contains an organic solvent, one or more organic solvents may be used in mixture form. In the present invention, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methyl-2-pyrrolidone, and cyclohexanone is particularly preferred, a developer containing at least one selected from the group consisting of cyclopentanone, γ-butyrolactone, and dimethyl sulfoxide is more preferred, and a developer containing cyclopentanone is particularly preferred.

[0321] When the developer contains an organic solvent, the content of the organic solvent relative to the total mass of the developer is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, and particularly preferably 90% by mass or more. Alternatively, the above content may be 100% by mass.

[0322] The developing solution may further contain other components. Examples of other components include known surfactants and known defoamers.

[0323] [Method of supplying developer] There are no particular restrictions on the method of supplying the developer as long as a desired pattern can be formed. These include immersing a substrate on which a film has been formed in the developer, paddle development in which the developer is supplied to the film formed on the substrate using a nozzle, or a method of continuously supplying the developer. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. From the viewpoint of developer penetration, removal of non-image areas, and manufacturing efficiency, a method of supplying the developer with a straight nozzle or a method of continuously supplying it with a spray nozzle is preferred, and from the viewpoint of developer penetration into the image area, a method of supplying with a spray nozzle is more preferred. In addition, a step may be adopted in which the developer is continuously supplied with a straight nozzle, the substrate is spun to remove the developer from the substrate, and after spin drying, the developer is supplied again with a straight nozzle, and the substrate is spun to remove the developer from the substrate. This step may be repeated multiple times. Examples of methods of supplying the developer in the development process include a step in which the developer is continuously supplied to the substrate, a step in which the developer is kept in a nearly stationary state on the substrate, a step in which the developer is vibrated on the substrate with ultrasound, etc., and a step that combines these.

[0324] The development time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the developer solution during development is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0325] In the developing process, after processing with the developer, the pattern may be further washed (rinsed) with a rinsing solution. Alternatively, methods such as supplying the rinsing solution before the developer in contact with the pattern dries completely may be employed.

[0326] [Rinsing Solution] If the developer is an alkaline aqueous solution, water can be used as the rinsing solution. If the developer contains an organic solvent, a solvent different from the solvent contained in the developer (for example, water, or an organic solvent different from the organic solvent contained in the developer) can be used as the rinsing solution.

[0327] When the rinsing solution contains an organic solvent, the organic solvent can be the same as the organic solvent exemplified above when the developer contains an organic solvent. Preferably, the organic solvent in the rinsing solution is different from the organic solvent in the developer, and more preferably, it is an organic solvent with lower pattern solubility than the organic solvent in the developer.

[0328] If the rinsing solution contains an organic solvent, one or more organic solvents may be used in mixture form. The organic solvents are preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, and PGME, more preferably cyclopentanone, γ-butyrolactone, dimethyl sulfoxide, PGMEA, and PGME, and even more preferably cyclohexanone and PGMEA.

[0329] When the rinsing solution contains an organic solvent, the amount of the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and even more preferably 90% by mass or more, relative to the total mass of the rinsing solution. Alternatively, the amount of the organic solvent may be 100% by mass, relative to the total mass of the rinsing solution.

[0330] The rinse solution may further contain other components. Examples of other components include known surfactants and known defoaming agents.

[0331] [Method of supplying rinsing solution] There are no particular restrictions on the method of supplying the rinsing solution as long as a desired pattern can be formed. These include immersing the substrate in the rinsing solution, supplying the rinsing solution to the substrate by pouring the solution, supplying the rinsing solution to the substrate with a shower, and continuously supplying the rinsing solution onto the substrate using means such as a straight nozzle. From the viewpoint of the penetration of the rinsing solution, the removal of non-image areas, and manufacturing efficiency, there are methods of supplying the rinsing solution with a shower nozzle, a straight nozzle, a spray nozzle, etc., and the method of continuous supply with a spray nozzle is preferred, and from the viewpoint of the penetration of the rinsing solution into the image area, the method of supplying with a spray nozzle is more preferred. There are no particular restrictions on the type of nozzle, and examples include straight nozzles, shower nozzles, spray nozzles, etc. That is, the rinsing process is preferably a process of supplying the rinsing solution to the film after exposure using a straight nozzle or continuously supplying it, and it is more preferable to supply the rinsing solution using a spray nozzle. Possible methods for supplying the rinsing solution in the rinsing process include a process in which the rinsing solution is continuously supplied to the substrate, a process in which the rinsing solution is kept in a nearly stationary state on the substrate, a process in which the rinsing solution is vibrated on the substrate using ultrasound or the like, and a process that combines these methods.

[0332] The rinsing time is preferably 10 seconds to 10 minutes, and more preferably 20 seconds to 5 minutes. The temperature of the rinsing solution during rinsing is not particularly specified, but is preferably 10 to 45°C, and more preferably 18 to 30°C.

[0333] <Heating Step> The pattern obtained by the developing step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a heating step in which the pattern obtained by the developing step is heated. That is, the method for producing a cured product of the present invention may include a heating step in which the pattern obtained by the developing step is heated. Furthermore, the method for producing a cured product of the present invention may include a heating step in which a pattern obtained by another method without performing a developing step, or a film obtained by a film formation step is heated. In the heating step, resins such as polyimide precursors are cyclized to become resins such as polyimide. In addition, crosslinking of unreacted crosslinkable groups in specific resins or crosslinking agents other than specific resins also proceeds. The heating temperature (maximum heating temperature) in the heating step is preferably 50 to 450°C, more preferably 150 to 350°C, even more preferably 150 to 250°C, even more preferably 160 to 250°C, and particularly preferably 160 to 230°C.

[0334] The heating step is preferably a step in which the heating promotes the cyclization reaction of the polyimide precursor within the pattern by the action of bases generated from the base generating agent.

[0335] In the heating process, heating is preferably carried out at a heating rate of 1 to 12°C / minute from the initial heating temperature to the maximum heating temperature. More preferably, the heating rate is 2 to 10°C / minute, and even more preferably 3 to 10°C / minute. By setting the heating rate to 1°C / minute or more, it is possible to prevent excessive volatilization of acid or solvent while ensuring productivity, and by setting the heating rate to 12°C / minute or less, it is possible to alleviate residual stress in the cured product. In addition, in the case of an oven capable of rapid heating, it is preferable to carry out heating at a heating rate of 1 to 8°C / second from the initial heating temperature to the maximum heating temperature, more preferably 2 to 7°C / second, and even more preferably 3 to 6°C / second.

[0336] The starting temperature for heating is preferably 20°C to 150°C, more preferably 20°C to 130°C, and even more preferably 25°C to 120°C. The starting temperature for heating refers to the temperature at which the process of heating to the maximum heating temperature is initiated. For example, when the resin composition of the present invention is applied to a substrate and then dried, this is the temperature of the film (layer) after drying, and it is preferable to start the heating process from a temperature 30 to 200°C lower than the boiling point of the solvent contained in the resin composition.

[0337] The heating time (heating time at the maximum heating temperature) is preferably 5 to 360 minutes, more preferably 10 to 300 minutes, and even more preferably 15 to 240 minutes.

[0338] In particular, when forming a multilayer laminate, from the viewpoint of interlayer adhesion, the heating temperature is preferably 30°C or higher, more preferably 80°C or higher, even more preferably 100°C or higher, and especially preferably 120°C or higher. The upper limit of the above heating temperature is preferably 350°C or lower, more preferably 250°C or lower, and even more preferably 240°C or lower.

[0339] Heating may be carried out in stages. For example, the process may involve raising the temperature from 25°C to 120°C at a rate of 3°C / min, holding at 120°C for 60 minutes, raising the temperature from 120°C to 180°C at a rate of 2°C / min, and holding at 180°C for 120 minutes. It is also preferable to treat the film while irradiating it with ultraviolet light, as described in U.S. Patent No. 9,159,547. Such a pretreatment process can improve the properties of the film. The pretreatment process is preferably carried out for a short time of about 10 seconds to 2 hours, and more preferably for 15 seconds to 30 minutes. The pretreatment process may consist of two or more steps; for example, the first pretreatment step may be carried out in the range of 100 to 150°C, followed by the second pretreatment step in the range of 150 to 200°C. Furthermore, the film may be cooled after heating, and in this case, the cooling rate is preferably 1 to 5°C / min.

[0340] The heating process is preferably carried out in a low-oxygen atmosphere, such as by flowing an inert gas like nitrogen, helium, or argon, or under reduced pressure, from the viewpoint of preventing the decomposition of specific resins. The oxygen concentration is preferably 50 ppm (by volume) or less, and more preferably 20 ppm (by volume) or less. The heating means in the heating process is not particularly limited, but examples include hot plates, infrared furnaces, electric ovens, hot air ovens, and infrared ovens.

[0341] <Post-development exposure step> The pattern obtained in the development step (or the pattern after rinsing, if a rinsing step is performed) may be subjected to a post-development exposure step in which the pattern after the development step is exposed, either in place of the heating step or in addition to the heating step. That is, the method for producing a cured product of the present invention may include a post-development exposure step in which the pattern obtained in the development step is exposed. The method for producing a cured product of the present invention may include a heating step and a post-development exposure step, or it may include only one of the heating step and the post-development exposure step. In the post-development exposure step, for example, reactions such as the cyclization of polyimide precursors etc. by photosensitivity of a photobase generator, or the elimination of acid-degradable groups by photosensitivity of a photoacid generator can be promoted. In the post-development exposure step, it is sufficient for at least a part of the pattern obtained in the development step to be exposed, but it is preferable for the entire pattern to be exposed. The amount of exposure in the post-development exposure step is 50 to 20,000 mJ / cm in terms of exposure energy at the wavelength to which the photosensitive compound is sensitive. ２ Preferably, 100 to 15,000 mJ / cm² ２ This is more preferable. The post-development exposure step can be performed, for example, using the light source in the exposure step described above, and it is preferable to use broadband light.

[0342] <Metal Layer Formation Process> The pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process) may be subjected to a metal layer formation process in which a metal layer is formed on the pattern. That is, the method for producing a cured product of the present invention preferably includes a metal layer formation process in which a metal layer is formed on the pattern obtained by the development process (preferably one that has been subjected to at least one of the heating process and the post-development exposure process).

[0343] The metal layer is not particularly limited, and existing metal species can be used, with examples including copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, tungsten, tin, silver, and alloys containing these metals, with copper and aluminum being more preferred, and copper being even more preferred.

[0344] The method for forming the metal layer is not particularly limited, and existing methods can be applied. For example, methods described in Japanese Patent Publication No. 2007-157879, Japanese Patent Publication No. 2001-521288, Japanese Patent Publication No. 2004-214501, Japanese Patent Publication No. 2004-101850, U.S. Patent No. 7,888,181, and U.S. Patent No. 9,177,926 can be used. For example, photolithography, PVD (physical vapor deposition), CVD (chemical vapor deposition), lift-off, electroplating, electroless plating, etching, printing, and methods combining these can be considered. More specifically, patterning methods combining sputtering, photolithography and etching, and patterning methods combining photolithography and electroplating can be mentioned. Preferred embodiments of plating include electroplating using copper sulfate or copper cyanide plating solutions.

[0345] The thickness of the metal layer is preferably 0.01 to 50 μm at the thickest part, and more preferably 1 to 10 μm.

[0346] <Applications> The manufacturing method of the cured product of the present invention, or the fields in which the cured product can be applied, include insulating films for electronic devices, interlayer insulating films for redistribution layers, and stress buffer films. Other applications include sealing films, substrate materials (base films and coverlays for flexible printed circuit boards, interlayer insulating films), or etching to form patterns on insulating films for the above-mentioned mounting applications. For more information on these applications, please refer to, for example, Science & Technology Co., Ltd., "High-Functionality and Application Technologies of Polyimides," April 2008, supervised by Masaaki Kakimoto; CMC Technical Library, "Fundamentals and Development of Polyimide Materials," November 2011; and the Japan Polyimide and Aromatic Polymer Research Association, ed., "Latest Polyimide Fundamentals and Applications," NTS, August 2010.

[0347] The method for manufacturing the cured product of the present invention, or the cured product of the present invention, can also be used for manufacturing printing plates such as offset plates or screen printing plates, for etching molded parts, and for manufacturing protective lacquers and dielectric layers in electronics, particularly microelectronics.

[0348] (Laminate and Method for Manufacturing a Laminate) The laminate of the present invention refers to a structure having multiple layers made of the cured product of the present invention. The laminate is a laminate containing two or more layers made of the cured product, and may be a laminate with three or more layers. Of the two or more layers made of the cured product included in the above laminate, at least one is made of the cured product of the present invention, and from the viewpoint of suppressing shrinkage of the cured product or deformation of the cured product due to the above shrinkage, it is also preferable that all the layers made of the cured product included in the above laminate are made of the cured product of the present invention.

[0349] In other words, the method for manufacturing the laminate of the present invention preferably includes a method for manufacturing the cured product of the present invention, and more preferably includes repeating the method for manufacturing the cured product of the present invention multiple times.

[0350] The laminate of the present invention preferably comprises two or more layers made of cured material, with a metal layer preferably included between any of the layers made of cured material. The metal layer is preferably formed by the metal layer formation step described above. That is, the method for manufacturing the laminate of the present invention preferably further includes a metal layer formation step of forming a metal layer on a layer made of cured material, which is performed multiple times during the manufacturing process of the cured material. The preferred embodiment of the metal layer formation step is as described above. As the laminate, for example, a laminate is preferred that includes at least three layers in which a first layer made of cured material, a metal layer, and a second layer made of cured material are laminated in this order. It is preferable that both the first layer made of cured material and the second layer made of cured material are layers made of cured material of the present invention. The resin composition of the present invention used to form the first layer made of cured material and the resin composition of the present invention used to form the second layer made of cured material may have the same composition or may have different compositions. The metal layer in the laminate of the present invention is preferably used as metal wiring such as a rewiring layer.

[0351] <Lamination Process> The method for manufacturing a laminate of the present invention preferably includes a lamination process. The lamination process is a series of steps that include performing, in this order, at least one of the following on the surface of a pattern (resin layer) or metal layer: (a) film formation process (layer formation process), (b) exposure process, (c) development process, (d) heating process, and post-development exposure process. However, the method may also involve repeating at least one of the following: (a) film formation process and (d) heating process and post-development exposure process. Furthermore, at least one of the following: (d) heating process and post-development exposure process may be followed by (e) metal layer formation process. Needless to say, the lamination process may further include the above-mentioned drying process and the like as appropriate.

[0352] If further lamination is performed after the lamination process, a surface activation treatment step may be performed after the exposure step, the heating step, or the metal layer formation step. Plasma treatment is an example of a surface activation treatment. Details of the surface activation treatment will be described later.

[0353] The above lamination process is preferably performed 2 to 20 times, and more preferably 2 to 9 times. For example, a configuration with 2 to 20 resin layers, such as resin layer / metal layer / resin layer / metal layer / resin layer / metal layer, is preferred, and a configuration with 2 to 9 resin layers is even more preferred. Each of the above layers may have the same composition, shape, film thickness, etc., or they may be different.

[0354] In the present invention, it is particularly preferable to form a cured product (resin layer) of the resin composition of the present invention so as to cover the metal layer after providing the metal layer. Specifically, examples include repeating the steps in the order of (a) film formation, (b) exposure, (c) development, (d) heating and post-development exposure, and (e) metal layer formation, or repeating the steps in the order of (a) film formation, (d) heating and post-development exposure, and (e) metal layer formation. By alternately performing the lamination step of stacking the resin composition layer (resin layer) of the present invention and the metal layer formation step, the resin composition layer (resin layer) and the metal layer of the present invention can be alternately stacked.

[0355] (Surface Activation Treatment Step) The manufacturing method of the laminate of the present invention preferably includes a surface activation treatment step in which at least a portion of the metal layer and the resin composition layer is surface activated. The surface activation treatment step is usually performed after the metal layer formation step, but after the development step (preferably after at least one of the heating step and the post-development exposure step), the surface activation treatment step may be performed on the resin composition layer before the metal layer formation step. The surface activation treatment may be performed only on at least a portion of the metal layer, or only on at least a portion of the resin composition layer after exposure, or on at least a portion of both the metal layer and the resin composition layer after exposure. It is preferable to perform the surface activation treatment on at least a portion of the metal layer, and more preferably to perform the surface activation treatment on a portion or all of the area on the surface of the metal layer where the resin composition layer is formed. By performing the surface activation treatment on the surface of the metal layer in this way, the adhesion with the resin composition layer (film) provided on its surface can be improved. It is also preferable to perform the surface activation treatment on a portion or all of the resin composition layer (resin layer) after exposure. Thus, by performing a surface activation treatment on the surface of the resin composition layer, the adhesion between the surface-activated layer and the metal layer or resin layer provided on the surface-activated layer can be improved. In particular, when the resin composition layer is cured, such as when performing negative type development, it is less susceptible to damage from the surface treatment and adhesion is easily improved. The surface activation treatment can be carried out, for example, by the method described in paragraph 0415 of International Publication No. 2021 / 112189. This content is incorporated herein by reference.

[0356] (Semiconductor Devices and Methods for Manufacturing the Same) The present invention also discloses semiconductor devices including a cured product or a laminate of the present invention. Furthermore, the present invention also discloses a method for manufacturing a semiconductor device including a method for manufacturing a cured product or a laminate of the present invention. Specific examples of semiconductor devices in which the resin composition of the present invention is used to form an interlayer insulating film for a redistribution layer can be found in paragraphs 0213 to 0218 and Figure 1 of Japanese Patent Application Publication No. 2016-027357, the contents of which are incorporated herein by reference.

[0357] (Resin) The resin of the present invention has a substructure represented by formula (A-3a) or a substructure represented by the following formula (A-3b), and the ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin is 80% or more. In formula (A-3a), X １ Y represents a cyclobutane ring. １ X represents a divalent organic group having at least one polymerizable group selected from the group consisting of (meth)acrylic group, vinylphenyl group, epoxy group, oxetane group, group having an ethylenically unsaturated bond, and maleimide group. In formula (A-3b), X １ Y represents a cyclobutane ring. １ R represents a divalent organic group having at least one polymerizable group selected from the group consisting of (meth)acrylic group, vinylphenyl group, epoxy group, oxetane group, group having an ethylenically unsaturated bond, and maleimide group, １ and R ２ Each of these independently represents a hydrogen atom or a monovalent organic group. It has a substructure represented by the following formula (A-2a) or formula (A-2b).

[0358] In the resin of the present invention, the total content of the substructure represented by formula (A-3a) or formula (A-3b) with respect to the total repeating units of the resin is preferably 50 mol% or more, more preferably 70 mol% or more, and particularly preferably 80 mol% or more.

[0359] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are based on mass.

[0360] [Purification of Acid Dianhydrides] <Purification of the acid dianhydride trans-cyclobutanetetracarboxylic acid dianhydride (trans-CBDA)> 50 g of cyclobutanetetracarboxylic acid dianhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., trans / cis = 75 / 25) was purified using a sublimation purifier SU-45-800 (manufactured by Asahi Seisakusho Co., Ltd.) at a sublimation temperature of 120°C, 2.4 × 10⁻¹⁶ －３ Pa (1.8 × 10) －５ By sublimation purification under the conditions of torr, 18.9 g of purified powder was obtained. The obtained powder was as follows: １ The structure was identified by 1H-NMR. The content of trans-CBDA in the cyclobutanetetracarboxylic dianhydride contained in the obtained powder was 100 mol%. １ H-NMR: trans-CBDA (C ２ D ３ N): δ3.86 (s, 4H)

[0361] <Purification of the acid dianhydride cis-cyclobutanetetracarboxylic dianhydride (cis-CBDA)> 20 g of the residue (origin portion) from the sublimation purification apparatus obtained above was added to 100 mL of acetonitrile, and 12.3 g of the resulting crystals were filtered off after recrystallization. The obtained powder was １ ¹H-NMR showed a trans / cis ratio of 7 / 93. The solution was again added to 100 mL of dibutyl ether, recrystallized, and the resulting crystals were filtered to obtain 3.2 g of purified powder. The obtained powder was as follows: １ The structure was identified by 1H-NMR. The content of cis-CBDA in the cyclobutanetetracarboxylic dianhydride contained in the obtained powder was 100 mol%. １ H-NMR: cis-CBDA (C ２ D ３ N): δ3.75 (d, 4H)

[0362] [Synthesis of Resins] -Synthesis of Polyimide A-1- In a nitrogen atmosphere, 19.6 g of trans-CBDA, 0.0 g of cis-CBDA, and 0.0 g of BPDA (3,3',4,4'-biphenyltetracarboxylic acid dianhydride) were added to a three-necked flask and dissolved in 500 mL of dimethylacetamide at 25°C. A 200 mL solution of dimethylacetamide containing 9.0 g of 4,4'-diaminodiphenyl ether and 9.6 g of 3,3'-dihydroxybenzidine was added dropwise over 1 hour to obtain a viscous solution of polyamic acid. After the dropwise addition was complete, the viscous solution was heated to 190°C and heated and stirred for a further 8 hours while distilling off the water generated in the Dean-Stark reaction to carry out the ring-closing reaction. The reaction mixture was cooled to 90°C, and 153 g of potassium carbonate, 16.8 g of chloromethylstyrene (trade name: CMS-P (substituted isomer mixture), manufactured by AGC Seimi Chemical Co., Ltd.), and 0.5 g of TEMPO (2,2,6,6-tetramethylpiperidine 1-oxyl) as a polymerization inhibitor were added and the mixture was stirred for a further 24 hours. Finally, 20 g of a 30% methanol solution of ethylamine was added as a terminal encapsulant and the mixture was left at room temperature for another hour. The resulting reaction mixture was diluted with 1 L of tetrahydrofuran and added dropwise to 5 L of vigorously stirred water to obtain the crude polyimide resin (A-1) of the present invention. This was dissolved again in 1 L of tetrahydrofuran, 50 g of ion exchange resin was added and the mixture was stirred at 25°C for 1 hour, the ion exchange resin was filtered off, and the polymer filtrate was added dropwise to 5 L of vigorously stirred water to obtain the resulting powder. This was dried under vacuum at 35°C for 24 hours to obtain 42.7 g of the polyimide resin (A-1) of the present invention. The weight-average molecular weight of the obtained polymer was 28,000, and the imidization rate was 100%.

[0363] -Synthesis of Polyimide A-13- In a nitrogen atmosphere, 7.45 g of trans-CBDA, 0.39 g of cis-CBDA, and 0.33 g of AA-8 (bisnorbornanoic acid dianhydride, trade name: BNBDA (ENEHYDE series, manufactured by ENEOS Corporation)) were added to a three-necked flask and dissolved in 500 mL of dimethylacetamide at 25°C. To this, a 200 mL solution of 2,2'-bis(trifluoromethyl)benzidine and 10.3 g of 2,2-bis(3-amino-4-hydroxyphenyl)propane in dimethylacetamide was added dropwise over 1 hour to obtain a viscous solution of polyamic acid. After the dropwise addition was complete, the reaction mixture was heated to 190°C and heated and stirred for a further 8 hours while distilling off the water generated at Dean-Stark to carry out the ring-closing reaction. The reaction solution was cooled to 90°C, and 182 g of potassium carbonate, 32.2 g of 2-(methanesulfonyloxy)ethyl methacrylate, and 0.5 g of TEMPO as a polymerization inhibitor were added, and the mixture was stirred for a further 24 hours. Finally, 1.5 g of N-(2-aminoethyl)maleimide was added as an end-capturing agent, and the mixture was stirred at room temperature for a further 1 hour. The resulting reaction solution was diluted with 1 L of tetrahydrofuran and added dropwise to 5 L of vigorously stirred water to obtain the crude polyimide resin (A-13) of the present invention. This was dissolved again in 1 L of tetrahydrofuran, 50 g of ion exchange resin was added, and the mixture was stirred at 25°C for 1 hour. The ion exchange resin was then filtered off, and the polymer filtrate was added dropwise to 5 L of vigorously stirred water to obtain the resulting powder. This was dried under vacuum at 35°C for 24 hours to obtain 39.8 g of the polyimide resin (A-13) of the present invention. The weight-average molecular weight of the obtained polymer was 28000, and the imidization rate was 100%.

[0364] -Synthesis of Polyimide Precursor (Polyamic Acid Ester) A-28- 19.6 g of trans-CBDA was added to a three-necked flask under a nitrogen atmosphere and dissolved in 300 mL of anhydrous tetrahydrofuran (water content less than 1 ppm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). 15.8 g of anhydrous pyridine (water content less than 1 ppm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 26.0 g of 2-hydroxyethyl methacrylate were added, and the mixture was heated and stirred at 50°C for 6 hours. Next, the reaction mixture was cooled to -10°C, and 24.0 g of thionyl chloride was added dropwise over 1 hour, and the reaction mixture was further stirred at 10°C for 2 hours. After cooling again to -10°C, a 100 mL solution of 19.5 g of 4,4'-diaminodiphenyl ether in tetrahydrofuran was slowly added dropwise, ensuring that the reaction temperature did not exceed 0°C. The mixture was stirred further at 0°C for 2 hours, and 10 mL of ethanol was added to stop the reaction and obtain the polyimide precursor solution of the present invention. This reaction solution was added dropwise to 5 L of vigorously stirred water to obtain the crude polyimide precursor (A-28). This was dissolved again in 1 L of tetrahydrofuran, 50 g of ion exchange resin was added, and the mixture was stirred at 25°C for 1 hour. The ion exchange resin was then filtered off, and the polymer filtrate was added dropwise to 5 L of vigorously stirred water to obtain the resulting powder. This was dried under vacuum at 35°C for 24 hours to obtain 62.5 g of the polyimide precursor (A-28) of the present invention. The weight-average molecular weight of the obtained polymer was 25,000, and the imidization rate was 0%.

[0365] - Synthesis of polyimide precursor (polyamic acid ester) A-32 - A-32 was obtained by the same method as in the synthesis of A-28, except that 17.6 g of trans-CBDA and 1.9 g of cis-CBDA were used instead of 19.6 g of trans-CBDA. - Synthesis of polyimide precursor (polyamic acid ester) A-35 - 4.7 g of trans-CBDA, 0.2 g of cis-CBDA, and 7.76 g of 4,4'-oxydiphthalic anhydride were added to a three-necked flask under a nitrogen atmosphere and dissolved in 300 mL of anhydrous tetrahydrofuran (water content less than 1 ppm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.). To this, 15.8 g of dehydrated pyridine (water content less than 1 ppm, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 26.0 g of 2-hydroxyethyl methacrylate were added, and the mixture was heated and stirred at 50°C for 6 hours. Next, the reaction solution was cooled to -10°C, and 19.2 g of thionyl chloride was added dropwise over 1 hour, and the reaction solution was further stirred at 10°C for 2 hours. After cooling again to -10°C, 100 mL of a tetrahydrofuran solution containing 10.6 g of 4,4'-diaminobenzophenone was slowly added dropwise, ensuring that the reaction temperature did not exceed 0°C. Stirring was continued at 0°C for 2 hours, and 10 mL of ethanol was added to stop the reaction and obtain the polyimide precursor solution of the present invention. This reaction solution was added dropwise to 5 L of vigorously stirred water to obtain the crude polyimide precursor (A-35). This was dissolved again in 1 L of tetrahydrofuran, 50 g of ion exchange resin was added, and the mixture was stirred at 25°C for 1 hour. The ion exchange resin was then filtered off, and the polymer filtrate was added dropwise to 5 L of vigorously stirred water to produce a powder, which was then filtered off. This powder was dried under vacuum at 35°C for 24 hours to obtain 38.8 g of the polyimide precursor (A-35) of the present invention. The weight-average molecular weight of the obtained polymer was 26,000, and the imidization rate was 0%.

[0366] In the examples below where "PI" is written in the "Type of Resin" column of the table, the acid anhydride, diamine, and crosslinkable group-containing diamine listed in the table were used, the polymerizable group was changed to the one listed in "Crosslinkable Group" in the table, and the terminal group was changed to the one listed in the table below, except that the synthesis was carried out in the same manner as described for polyimide A-1 above. The values ​​in the table represent the molar ratio of each raw material used. In the examples below where "PA" is written in the "Type of Resin" column of the table, the acid anhydride, diamine, and crosslinkable group-containing diamine listed in the table were used, the polymerizable group was changed to the one listed in "Crosslinkable Group" in the table, and the terminal group was changed to the one listed in the table below, except that the synthesis was carried out in the same manner as described for polyimide precursor A-28 above. Note that the crosslinkable group-containing diamine has a structure consisting of DAK-X (X=1 to 3), a crosslinkable group, and a linking group X. For example, in resin A-1, the crosslinkable group-containing diamine has a structure in which the crosslinkable group (K-3) and the linking group X (-O-) form an -O- linkage (ether linkage) as X in formula (DAK-1). Also, in resin A-45, the crosslinkable group-containing diamine has a structure in which the crosslinkable group (K-1) and the linking group X (-CO) form an -O- linkage (ether linkage) as X in formula (DAK-1). ２ The -) structure forms a -C(=O)O- linkage (ester linkage) and has an -Ar-C(=O)O- structure. In the table, examples where "CO2" is written in the "Poly-CO2- / Poly-NH-" column indicate that the terminal end after the polycondensation reaction of the raw materials is a structure derived from an acid anhydride, and examples where "NH" is written indicate that the terminal end after the reaction of the raw materials is a structure derived from a diamine. For example, if you want to obtain a resin whose terminal end is a structure derived from an acid anhydride as described above, one possible method is to use an amount of acid anhydride or a compound derived from an acid anhydride that is greater than the amount of diamine or a compound derived from a diamine during synthesis. By reacting these structures with an end-sealing agent, the structure derived from the end-sealing agent is linked to the end of the resin as the structure described in the "End Group" column of the table by the "CO2" structure or "NH".

[0367] [Measurement Method for Weight-Average Molecular Weight] Unless otherwise specified, the weight-average molecular weight and number-average molecular weight for each resin were measured using the following method. A high-speed GPC instrument HLC-8420GPC (manufactured by Tosoh Corporation) was used, with a TSK guard column Super AW-H (4.6 mm × 35 mm) as the guard column and two TSKgel Super AWM-H (4.6 mm × 150 mm) columns connected in series for GPC measurement. A 0.01 mol / L lithium bromide NMP (N-methyl-2-pyrrolidone) solution was used as the eluent. The measured weight-average molecular weight is listed in the "Mw" column in the table.

[0368] [Method for measuring the imidization rate] Each resin was dissolved in γ-butyrolactone, diluted to 2,000 mPa·s, and applied to a silicon wafer by spin coating to form a resin layer. The silicon wafer to which the obtained resin layer was applied was dried on a hot plate at 110°C for 5 minutes to obtain a resin layer with a uniform thickness of approximately 15 μm on the silicon wafer after film formation. The above resin layer was measured by the ATR method using Nicoleti S20 (Thermofisher), with a measurement range of 4000 to 700 cm². －１ The measurement was taken 50 times. 1380 cm －１ Nearby (1350-1450 cm) －１ (If there are multiple peaks, the peak height of the one with the highest peak intensity) and 1500 cm －１ Nearby (1460-1550 cm) －１ The imidization index A of the resin was calculated by dividing the value by the peak height of the peak with the highest peak intensity (if there are multiple peaks). For films heated at 350°C for 1 hour under a nitrogen atmosphere at a heating rate of 10°C / min, the imidization index B was calculated using the same method, and the imidization rate of the resin was calculated by dividing the imidization index A by the imidization index B.

[0369]

[0370]

[0371]

[0372]

[0373]

[0374]

[0375] <Examples and Comparative Examples> In each example, the components listed in the table below were mixed with 0.02 parts by mass of Adeka Stab AO-20 (manufactured by ADEKA Corporation) as an antioxidant, 0.03 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 0.02 parts by mass of epoxy silane coupling agent KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.) or 0.03 parts by mass of acrylic silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.) as adhesives to obtain each resin composition. Furthermore, in each comparative example, the components listed in the table below were mixed with 0.02 parts by mass of ADEKA stab AO-20 (manufactured by ADEKA Corporation) as an antioxidant, 0.03 parts by mass of p-methoxyphenol as a polymerization inhibitor, and 0.02 parts by mass of epoxy silane coupling agent KBM-403 (manufactured by Shin-Etsu Silicone Co., Ltd.) and 0.03 parts by mass of acrylic silane coupling agent KBM-503 (manufactured by Shin-Etsu Silicone Co., Ltd.) as adhesives to obtain each comparative resin composition. Specifically, the content of each component listed in the table is the amount (parts by mass) indicated in the "parts" column of each column in the table. Also, if multiple materials are listed in the same column, it indicates that each material was mixed in equal mass. The obtained resin compositions and comparative resin compositions were pressure filtered using a polytetrafluoroethylene filter with a pore width of 0.5 μm. Also, in the table, "-" indicates that the resin composition does not contain the corresponding component. After applying the resin composition of each example to a silicon wafer, a film with a thickness of 10 μm was formed by drying at 100°C for 5 minutes, and the transmittance of light at a wavelength of 365 nm was measured. In all cases, the transmittance was 15% or more. The measurement was performed using an ultraviolet-visible spectrophotometer (Hitachi UH-4150).

[0376]

[0377] Details of each component listed in the table are as follows:

[0378] [Resin] ・A-1 to A-46: A-1 to A-46 synthesized as described above ・CA-1 to CA-8: CA-1 to CA-8 synthesized as described above

[0379] [Polymerizable Compounds] ・C-1 to C-5: Compounds with the following structures ・C-6: NK Ester 4G (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・C-7: NK Ester A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・C-8: NK Ester BPE-500 (manufactured by Shin-Nakamura Chemical Co., Ltd.) ・C-9: NK Ester A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)

[0380] [Photopolymerization initiators] ・b-1 to b-14: Compounds with the following structures ・b-15: TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-3 46. ​​Isomass mixture of TR-PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610 (all manufactured by TRONLY) - b-16: Isomass mixture of NCI-730, NCI-831E, NCI-930 (all manufactured by ADEKA) - b-17 to b-18: Compounds with the following structure

[0381] [Sensitizers] ・z-1: SPEEDCURE DETX (Sartomer Co., Ltd.) ・z-2: SPEEDCURE EAQ (Sartomer Co., Ltd.) ・z-3: SPEEDCURE EMK (Sartomer Co., Ltd.) ・z-4: NF-CO01 (Nippon Chemical Industries, Ltd.) ・z-5: NF-PY02 (Nippon Chemical Industries, Ltd.) ・z-6: 9,10-Dibutoxyanthracene

[0382] [Base Generators] ・F-1 to F-5: Compounds with the following structure

[0383] [Additives] ・T-1 to T-8: Compounds with the following structure ・t-1 to t-4: Compounds with the following structure

[0384] [Solvents] ・S-1: γ-butyrolactone (GBL) ・S-2: γ-valerolactone (GVL) ・S-3: dimethyl sulfoxide (DMSO) ・S-4: N-methylpyrrolidone (NMP) ・S-5: cyclopentanone (CPX) ・S-6: propylene glycol monomethyl ether acetate (PGMEA) ・S-7: MDMPA (KJCMPA-100 (manufactured by KJ Chemicals Co., Ltd.)) ・S-8: ethyl lactate

[0385] <Evaluation> [Evaluation of curability] The resin compositions prepared in each example and comparative example were applied in layers to a copper substrate by spin coating to form a resin composition layer. The copper substrate on which the resin composition layer was formed was dried on a hot plate at 100°C for 5 minutes to obtain a resin composition layer on the copper substrate with a thickness of 19.2 μm and a nearly uniform thickness. The resin composition layer on the copper substrate was exposed to light at a wavelength of 365 nm with an exposure energy of 50 to 2000 mJ / cm2 in increments of 10 mJ / cm2 using a photomask on which a 10 μm 1:1 line and space pattern was formed. After that, it was developed with cyclopentanone for 60 seconds, rinsed with PGMEA, and then cured at 220°C for 5 min to obtain a cured product with a 1:1 line and space pattern. The line pattern of the obtained cured product was observed using a scanning electron microscope (SEM) to determine the optimal exposure amount for forming a 10 μm 1:1 line and space pattern. Lower exposure is preferable as it results in higher sensitivity. A, B, or C is particularly preferable. -Evaluation Criteria- A: Optimal exposure is 100 mJ / cm ２ It was less than . B: Optimal exposure dose is 100 mJ / cm ２ More than 200mJ / cm ２ It was less than . C: Optimal exposure dose is 200 mJ / cm ２ More than 500mJ / cm ２ It was less than . D: Optimal exposure dose is 500 mJ / cm ２ More than 1000mJ / cm ２ It was less than . E: Optimal exposure dose is 1000 mJ / cm ２ That was all.

[0386] [Evaluation of Developability] The resin compositions prepared in each example and comparative example, or the comparative resin composition, were applied in layers to a copper substrate by spin coating to form a resin composition layer or a comparative resin composition layer. The copper substrates on which the obtained resin composition layers or comparative resin composition layers were formed were dried on a hot plate at 100°C for 5 minutes to obtain a resin composition layer or comparative resin composition layer with a thickness of 19.2 μm and a nearly uniform thickness on the copper substrate. The resin composition layer or comparative resin composition layer on the copper substrate was subjected to development at 500 mJ / cm using a photomask with a 1:1 line and space pattern formed in 1 μm increments from 5 μm to 25 μm. ２ The samples were exposed to light with a wavelength of 365 nm using the specified exposure energy. In the cases where "M" was indicated in the exposure conditions column, a stepper was used as the light source, and the samples were exposed to light with the exposure wavelength (nm) indicated in the "Exposure Wavelength (nm)" column of the table. Subsequently, the samples were developed with cyclopentanone for 60 seconds and rinsed with PGMEA to obtain a 100 μm square resin layer. In the cases where a numerical value was indicated in the "Cure Temperature" column, a hot plate was used to heat the resin composition layer after exposure in a nitrogen atmosphere at a heating rate of 10 °C / min until it reached the temperature indicated in the "Cure Temperature (°C)" column of the table. After that, the temperature was maintained for the "Cure Time (min)" time indicated in the table to obtain a cured product. The line pattern of the obtained cured product was observed using a scanning electron microscope (SEM), and the number of residues with a maximum diameter of 1 μm or more in the 10 μm square developed area at 10 μmL / S was measured at five different locations, and the average value was calculated. The evaluation was conducted according to the following evaluation criteria, and the evaluation results are recorded in the "Developability" column of the table. The fewer the observed residues, the better the developability. -Evaluation Criteria- A: The average number of residues was 0. B: The average number of residues was 0 or more and less than 1. C: The average number of residues was 1 or more and less than 2. D: The average number of residues was 2 or more and less than 5. E: The average number of residues was 5 or more.

[0387] [Evaluation of Adhesion] In each example and comparative example, cured products were obtained using the same method as described in "Evaluation of Developability" above. The line patterns of the cured products were observed using a scanning electron microscope (SEM), and the line width at which peeling began to occur in L / S of 5 to 25 μm was observed. The evaluation was performed according to the evaluation criteria below, and the evaluation results are recorded in the "Adhesion" column of the table. Products that adhere well even at narrow line widths are considered to have superior adhesion. -Evaluation Criteria- A: No peeling was observed at any line width. B: Peeling was observed at 5 μm, but not at 10 μm or wider. C: Peeling was observed at 10 μm or narrower, but not at 15 μm or wider. D: Peeling was observed at 15 μm or narrower, but not at 20 μm or wider. E: Peeling was observed even at 20 μm or wider.

[0388] [Evaluation of CTE (Coefficient of Thermal Expansion)] In each example and comparative example, a resin composition or a comparative resin composition was applied to a silicon wafer by spin coating to form a resin composition layer. The silicon wafer to which the obtained resin composition layer was applied was dried on a hot plate at 110°C for 5 minutes to obtain a resin composition layer with a uniform thickness of 19.2 μm after film formation on the silicon wafer. The obtained resin composition layer was subjected to a Ushio exposure machine (light source: 500 W / m²). ２ (Ultra-high pressure mercury lamp) 400 mJ / cm ２Exposure was performed using a dumbbell-shaped mask with the following exposure energy. The dumbbell shape was the No. 7 dumbbell shape described in JIS K 6251:2017. The resin composition layer (resin layer) after exposure was developed with cyclopentanone until the unexposed areas were removed, and then rinsed with PGMEA for 30 seconds. Furthermore, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C / min to 230°C for 3 hours. The cured resin layer (cured product) was immersed in a 4.9 mass% hydrofluoric acid aqueous solution, and the dumbbell-shaped cured product (test piece) was peeled off from the silicon wafer (sample width 2 mm, sample length 35 mm). The CTE of the test piece prepared above at 25°C to 125°C was measured using a TMA450 (TA Instruments). The heating and cooling conditions during evaluation were as follows (1) to (4). (1) The temperature was increased from room temperature to 130°C at a heating rate of 5°C / min. (2) The temperature was lowered from 130°C to 10°C at a rate of 5°C / min. (3) The temperature was raised from 10°C to 300°C at a rate of 5°C / min. (4) The sample was allowed to cool naturally to room temperature. During the heating and cooling processes in (1) to (4) above, the elongation (displacement) of the sample was measured, and the elongation (displacement) of the sample at 25°C and 125°C in process (3) was divided by the temperature to calculate the coefficient of thermal expansion. (Example: If the length of the sample at 25°C was 50 mm and the length of the sample at 125°C was 50.2 mm, the displacement was calculated to be 0.4% = 4000 ppm, and the coefficient of thermal expansion was calculated to be 4000 / (125 - 25) = 40 ppm / °C.) The obtained coefficient of thermal expansion was evaluated according to the following evaluation criteria, and the evaluation results are recorded in the "CTE" column of the table. -Evaluation Criteria- A: The coefficient of thermal expansion was less than 20 ppm / °C. B: The coefficient of thermal expansion was 20 ppm / °C or higher and less than 30 ppm / °C. C: The coefficient of thermal expansion was 30 ppm / °C or higher and less than 50 ppm / °C. D: The coefficient of thermal expansion was 50 ppm / °C or higher and less than 65 ppm / °C. E: The coefficient of thermal expansion was 65 ppm / °C or higher.

[0389] From the above results, it can be seen that the resin composition according to the present invention has excellent curability. In comparison, it can be seen that the cured product obtained from the comparative composition that does not contain the specific resin has inferior curability.

[0390] <Example 1001> The resin composition used in Example 1 was applied in layers to the surface of a copper thin layer formed on a resin substrate by spin coating, and dried at 100°C for 4 minutes to form a photosensitive resin composition layer with a thickness of 20 μm. Then, it was exposed using a stepper (Nikon Corporation, NSR1505 i6). Exposure was performed at a wavelength of 365 nm through a mask (a binary mask with a 1:1 line-and-space pattern and a line width of 10 μm). After exposure, it was heated at 100°C for 4 minutes. After the above heating, it was developed with cyclohexanone for 2 minutes and rinsed with PGMEA for 30 seconds to obtain the layer pattern. Next, under a nitrogen atmosphere, the temperature was increased at a rate of 10°C / min until it reached 230°C, and then maintained at 230°C for 3 hours to form an interlayer insulating film for the redistribution layer. This interlayer insulating film for the redistribution layer had excellent insulating properties. Furthermore, when semiconductor devices were manufactured using these interlayer insulating films for redistribution layers, it was confirmed that they functioned without any problems.

[0391] <Examples 1002 to 1046> In Example 1001, the resin composition was changed from the one used in Example 1 to the one used in Examples 2 to 46, respectively. Otherwise, the evaluation was the same as in Example 1001. In all examples, the interlayer insulating film for the redistribution layer had excellent insulating properties. The semiconductor device operated without problems.

Claims

1. A resin composition comprising a polymerizable resin and a photopolymerization initiator, wherein the resin has at least one of a substructure represented by formula (A-1a) and a substructure represented by formula (A-1b), and the ratio of the molar amount of cyclobutane rings in a trans conformation to the total molar amount of cyclobutane rings contained in the resin is 80% or more. In formula (A-1a), X １ Y represents a cyclobutane ring. １ represents a divalent organic group. In formula (A-1b), X １ Y represents a cyclobutane ring. １ R indicates a divalent organic group, １ and R ２ Each of these independently represents either a hydrogen atom or a monovalent organic group.

2. The resin composition according to claim 1, wherein the ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin is 95 to 99%.

3. The resin composition according to claim 1, wherein the total content of the substructure represented by formula (A-1a) or formula (A-1b) relative to the total repeating units in the resin is 50 mol% or more.

4. The resin contains at least one partial structure selected from the group consisting of a partial structure represented by formula (A-11), a partial structure represented by formula (A-12), formula (A-13), and a partial structure represented by formula (A-14). In formula (A-11), X １１ represents a cyclobutane ring. In formula (A-12), X １１ represents a cyclobutane ring, R １ and R ２ each represent a hydrogen atom or a monovalent organic group. In formula (A-13), X １１ represents a cyclobutane ring, R １ each represent a hydrogen atom or a monovalent organic group. In formula (A-14), X １１ represents a cyclobutane ring, R ２ each represent a hydrogen atom or a monovalent organic group. Among all X １１ contained in the resin, the proportion of the molar amount of the cyclobutane ring in the trans conformation is 80 mol% or more. The resin composition according to claim 1.

5. The resin composition according to claim 1, wherein the resin has a substructure represented by formula (A-1a), and the substructure represented by formula (A-1a) has a substructure represented by the following formulas (A-2a1) and (A-2b1). In equation (A-2a1), Ya ２ The structure is represented by the following formula (Y-1), and Ay ２ represents the base shown in equation (Z-1), where n2 is an integer of 1 or 2. In equation (A-2b1), Yb ２ This represents the structure shown by the following formula (Y-2). In formula (Y-1), Ar １ L represents an aromatic group having 6 to 10 carbon atoms, which may have substituents. １ The bond is a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ - or -CR ４ ２ - indicates Y １ Ar represents an aromatic group having 6 to 30 carbon atoms, which may have substituents. １ and Y １ At least one of them is Ay as a substituent. ２ It has bonding sites with, where a represents an integer from 0 to 3, and * represents the bonding site with the nitrogen atom. In formula (Y-2), Ar ２ L represents an aromatic group having 6 to 10 carbon atoms, which may have substituents. ２ The bond is a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ - or -NR ３ (C=O)NR ２ - indicates Y ２ represents an aromatic group having 6 to 30 carbon atoms, which may have substituents, b represents an integer from 0 to 3, and * represents a bonding site with a nitrogen atom. In formula (Z-1), Lx １ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates Lx ２ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates R １ R represents a hydrogen atom or a monovalent organic group. ２ R represents a hydrogen atom or a monovalent organic group. ３ R represents a hydrogen atom or a monovalent organic group. ４ R represents a hydrogen atom or a monovalent organic group. ５ represents a monovalent organic group, La represents the group shown in the following formula (La-1), Lb represents a C1-C12 r4+1valent hydrocarbon group, a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r1 represents 0 or 1, r2 represents 0 or 1, r3 represents an integer from 0 to 5, r4 represents an integer from 1 to 10, and * represents Ar of formula (Y-1). １ or Y １ This shows the binding site. In formula (La-1), Ra １ , Ra ２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and * represents Lx １ The wavy line indicates the connection point, Lx ２ The binding sites with either Lb or A are shown, respectively. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z each independently represent an integer from 1 to 30.

6. The resin composition according to claim 1, wherein the resin has a partial structure represented by the following formula (A-2a2) and a partial structure represented by the following formula (A-2b2) as the partial structure represented by the formula (A-1b). In the formula (A-2a2), Ya ２ represents a structure represented by the following formula (Y-3), and R ５１ , R ５２ , Ay ３ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or the following formula (Z-2). n3 is an integer of 0 to 3, and when n3 = 0, at least one of R ５１ , R ５２ represents a group represented by the formula (Z-2). In the formula (A-2b2), Yb ２ represents a divalent organic group, and R ５１ , R ５２ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group or the following formula (Z-2). In the formula (Y-3), Ar ３ represents an aromatic group having 6 to 10 carbon atoms which may have a substituent, and L ３ represents a single bond, -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, or, -NR ３ (C=O)NR ２ -. Y ３ represents an aromatic group having 6 to 30 carbon atoms which may have a substituent, and at least one of Ar ３ and Y ３ has a bonding site with Ay ３ as a substituent, a represents an integer of 0 to 3, and * represents a bonding site with a nitrogen atom. In the formula (Z-2), Lx １ is -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates Lx ２ -O-, -NR １ -, -(C=O)O-, -O(C=O)-, -O(C=O)O-, -(C=O)NR ２ -, -NR ２ (C=O)-, -NR ２ (C=O)O-, -O(C=O)NR ２ -, -NR ２ (C=O)NR ３ -, -NR ３ (C=O)NR ２ -ien-CH ２ CH(OH)-CH ２ -, or -CH ２ CH(OR ５ ) - CH ２ - indicates R １ R represents a hydrogen atom or a monovalent organic group. ２ R represents a hydrogen atom or a monovalent organic group. ３ R represents a hydrogen atom or a monovalent organic group. ４ R represents a hydrogen atom or a monovalent organic group. ５ represents a monovalent organic group, La represents the group shown in the following formula (La-1), Lb represents a C1-C12 r4+1 valent hydrocarbon group, a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3), A represents an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r1 represents 0 or 1, r2 represents 0 or 1, r3 represents an integer from 0 to 5, r4 represents an integer from 1 to 10, and * represents Ar of formula (Y-3). ３ or Y ３ This shows the binding site. In formula (La-1), Ra １ , Ra ２ Each of these independently represents a hydrogen atom, an alkyl group, or an aryl group, and * represents Lx １ The wavy line indicates the connection point, Lx ２ The binding sites with either Lb or A are shown, respectively. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z each independently represent an integer from 1 to 30.

7. The resin composition according to claim 1, wherein the resin has a structure represented by the following formula (M-1) or (M-2). In formula (M-1) or formula (M-2), L １ L represents an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a group consisting of any or a combination of the following formulas (Lb-1) to (Lb-3). ２ R indicates a single bond or an organic group with (k+1) valency. ２１ represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, A represents a group containing any of the following: an epoxy group, an oxetanyl group, or a group having an ethylenically unsaturated bond, r represents 0 or 1, k represents an integer from 1 to 6, and * represents Y １ This shows the binding site. In formulas (Lb-1) to (Lb-3), Lc1 represents an alkylene group having 2 to 12 carbon atoms, an arylene group having 6 to 18 carbon atoms, or a combination thereof, and x, y, and z represent integers from 0 to 30.

8. L in the above formula (M-1) or (M-2) １ The resin composition according to claim 7, wherein the resin composition is represented by any one of the formulas (Lb-1), (Lb-2), or (Lb-3), or a combination thereof.

9. The resin contains Y in formula (A-1a) or formula (A-1b). １ The resin composition according to claim 1, comprising at least one of the structures represented by the following formula (Y1-1) or formula (Y1-2). In equation (Y1-1), Ay １１ and Ay １２ Each independently represents a group having a polymerizable group, and m1 and m2 independently represent integers from 0 to 2, R ２１ and R ２２ Each of these independently represents one of an alkyl group, an aryl group, a halogen atom, or a trifluoromethyl group, n1 is an integer from 0 to (4-m1), n2 is an integer from 0 to (4-m2), and L is a single bond, -CR １ R ２ -, -C=C-, -O-, -(C=O)-, -NH-(C=O)-, -(C=O)O-, -S(=O)-, -S(=O) ２ - indicates R １ and R ２ Each of the following independently represents a hydrogen atom, an alkyl group, an aryl group, or a trifluoromethyl group, and * indicates a bonding site with other structures. In formula (Y1-2), Ay １３ indicates a group having a polymerizable group, m3 is an integer from 0 to 2, and R ２３ represents one of the alkyl group, aryl group, halogen atom, or trifluoromethyl group, n3 is an integer from 0 to (4-m3), and * indicates a bonding site with other structures.

10. The resin composition according to any one of claims 1 to 9, wherein the photopolymerization initiator is a photoradical polymerization initiator.

11. The resin composition according to any one of claims 1 to 9, wherein the photopolymerization initiator is a (keto)oxime ester compound.

12. The resin composition according to any one of claims 1 to 9, comprising a polyfunctional polymerizable compound different from the resin.

13. A resin composition according to any one of claims 1 to 9, comprising an amine compound.

14. A resin composition according to any one of claims 1 to 9, used for forming an interlayer insulating film for a redistribution layer.

15. A cured product obtained by curing the resin composition according to any one of claims 1 to 9.

16. A laminate comprising two or more layers made of the cured product described in claim 15, wherein a metal layer is included between any of the layers made of the cured product.

17. A method for producing a cured product, comprising a film-forming step of applying a resin composition according to any one of claims 1 to 9 onto a substrate to form a film.

18. A method for producing a cured product according to claim 17, comprising an exposure step of selectively exposing the film and a developing step of developing the film using a developer to form a pattern.

19. A method for producing a cured product according to claim 17, comprising a heating step of heating the film to 50 to 450°C.

20. A method for manufacturing a laminate, comprising the method for manufacturing a cured product according to claim 17.

21. A method for manufacturing a semiconductor device, comprising the method for manufacturing a cured product according to claim 17.

22. A semiconductor device comprising the cured product described in claim 15.

23. A resin having a substructure represented by formula (A-3a) or a substructure represented by formula (A-3b), wherein the ratio of the molar amount of cyclobutane rings in the trans conformation to the total molar amount of cyclobutane rings contained in the resin is 80% or more. In formula (A-3a), X １ Y represents a cyclobutane ring. １ X represents a divalent organic group having at least one polymerizable group selected from the group consisting of (meth)acrylic group, vinylphenyl group, epoxy group, oxetane group, group having an ethylenically unsaturated bond, and maleimide group. In formula (A-3b), X １ Y represents a cyclobutane ring. １ R represents a divalent organic group having at least one polymerizable group selected from the group consisting of (meth)acrylic group, vinylphenyl group, epoxy group, oxetane group, group having an ethylenically unsaturated bond, and maleimide group, １ and R ２ Each of these independently represents either a hydrogen atom or a monovalent organic group.

24. The resin according to claim 23, wherein the total content of the substructure represented by formula (A-3a) or formula (A-3b) is 50 mol% or more with respect to the total repeating units of the resin.

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